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特開2017-95435有機化合物、光変調組成物、およびそれを用いる光変調デバイス
(19)【発行国】日本国特許庁(JP)
(12)【公報種別】公開特許公報(A)
(11)【公開番号】特開2017-95435(P2017-95435A)
(43)【公開日】2017年6月1日
(54)【発明の名称】有機化合物、光変調組成物、およびそれを用いる光変調デバイス
(51)【国際特許分類】
C07C 233/43 20060101AFI20170428BHJP
G02F 1/15 20060101ALI20170428BHJP
C07C 233/62 20060101ALI20170428BHJP
C09K 9/02 20060101ALI20170428BHJP
C07D 209/48 20060101ALI20170428BHJP
【ＦＩ】
C07C233/43CSP
G02F1/15 505
C07C233/62
C09K9/02 A
C07D209/48
【審査請求】有
【請求項の数】9
【出願形態】ＯＬ
【外国語出願】
【全頁数】69
(21)【出願番号】特願2015-256675(P2015-256675)
(22)【出願日】2015年12月28日
(31)【優先権主張番号】104138432
(32)【優先日】2015年11月20日
(33)【優先権主張国】TW
(71)【出願人】
【識別番号】390023582
【氏名又は名称】財團法人工業技術研究院
【氏名又は名称原語表記】ＩＮＤＵＳＴＲＩＡＬ ＴＥＣＨＮＯＬＯＧＹ ＲＥＳＥＡＲＣＨ ＩＮＳＴＩＴＵＴＥ
(74)【代理人】
【識別番号】100108833
【弁理士】
【氏名又は名称】早川 裕司
(74)【代理人】
【識別番号】100162156
【弁理士】
【氏名又は名称】村雨 圭介
(72)【発明者】
【氏名】▲きょう▼ 宇睿
(72)【発明者】
【氏名】黄 莉▲てい▼
(72)【発明者】
【氏名】呂 奇明
【テーマコード（参考）】
2K101
4C204
4H006
【Ｆターム（参考）】
2K101AA22
2K101DA01
2K101DB01
2K101DB31
2K101DC01
2K101DC45
2K101EB01
2K101EC11
2K101EE01
4C204BB05
4C204CB04
4C204DB30
4C204EB03
4C204FB16
4C204GB01
4H006AA01
4H006AB92
4H006BJ20
4H006BJ50
4H006BP30
4H006BU46
4H006BV25
4H006BV64
(57)【要約】 （修正有）
【課題】有機化合物、光変調組成物、およびそれを用いる光変調デバイスを提供する。【解決手段】有機化合物は式（Ｉ）で表される化学構造を有する。有機化合物はそのニュートラル状態において透明である。芳香族アミンに導入されたアミド基またはイミド基は、有機化合物の溶媒への溶解性を高めるだけでなく、有機化合物の電気化学的安定性をも高める。
（Ｘは、
；Ａｒはトリフェニルアミノ基等；Ｒ１はアルキル；Ｒ３はＨ、アルキル等；Ｒ４はＨ又はメチル等）
【選択図】図１
【特許請求の範囲】
【請求項1】
式（Ｉ）で定義される構造を有する有機化合物。
（式中、Ｘは、
または
であり、Ｒ１はアルキルであり、Ｒ３はＨ、アルキル、またはアルコキシであり、Ｒ４はＨまたはメチルであり、Ａｒは、
または
であり、Ａｒ’は、
または
であり、Ａｒ”は、
または
であり、Ａｒ３は、
または
であり、Ｒ２はＨ、アルキルまたはアルコキシである。）
【化1】
（式中、Ｘは、
【化2】
【化3】
【化4】
【化5】
【化6】
または
【化7】
であり、Ｒ１はアルキルであり、Ｒ３はＨ、アルキル、またはアルコキシであり、Ｒ４はＨまたはメチルであり、Ａｒは、
【化8】
または
【化9】
であり、Ａｒ’は、
【化10】
【化11】
【化12】
【化13】
【化14】
または
【化15】
であり、Ａｒ”は、
【化16】
【化17】
または
【化18】
であり、Ａｒ３は、
【化19】
【化20】
【化21】
【化22】
【化23】
または
【化24】
であり、Ｒ２はＨ、アルキルまたはアルコキシである。）
【請求項2】
Ｒ１はＣ１−８アルキル基であり、Ｒ２は水素、Ｃ１−８アルキル基、またはＣ１−８アルコキシ基であり、Ｒ３は水素、Ｃ１−８アルキル基、またはＣ１−８アルコキシ基である請求項１に記載の有機化合物。
【請求項3】
前記化合物が次式により表される請求項１に記載の有機化合物。
または
（式中、Ｒ５はＣ１−８アルキル基であり、Ｒ４はＣ１−８アルキル基であり、Ｒ６はＣ１−８アルキル基である。）
【化25】
【化26】
【化27】
または
【化28】
（式中、Ｒ５はＣ１−８アルキル基であり、Ｒ４はＣ１−８アルキル基であり、Ｒ６はＣ１−８アルキル基である。）
【請求項4】
第１の酸化性化合物であって、請求項１に記載された第１の酸化性化合物と、
還元性化合物と、
電解質と、
溶媒と、
を含む光変調組成物。
還元性化合物と、
電解質と、
溶媒と、
を含む光変調組成物。
【請求項5】
前記電解質が有機アルミニウム塩または無機リチウム塩である請求項４に記載の光変調組成物。
【請求項6】
前記酸化性化合物と前記電解質とのモル比が１：１から１：２０であり、前記還元性化合物と前記電解質とのモル比が１：１から１：２０であり、かつ前記電解質の濃度が０．０１Ｍから１．５Ｍの間である請求項４に記載の光変調組成物。
【請求項7】
前記還元性化合物が、下記の化合物からなる群より選ばれる請求項４に記載の光変調組成物。
および
【化29】
【化30】
および
【化31】
【請求項8】
下記の化合物からなる群より選ばれる第２の酸化性化合物をさらに含む請求項４に記載の光変調組成物。
および
（式中、Ｒ８はＨまたはアルキルである。）
【化32】
【化33】
【化34】
【化35】
および
【化36】
（式中、Ｒ８はＨまたはアルキルである。）
【請求項9】
その表面上に第１の透明導電層を備えた第１の透明基板、および
その表面上に第２の透明導電層を備えた第２の透明基板を含み、前記第１の透明導電層および前記第２の透明導電層を互いに対面するように配置することにより設けられた一対の電極と、
前記第１および第２の透明導電層の間に挿入されてセルを形成する絶縁ユニットと、
前記セル中に充填された光変調組成物と、
を含む光変調デバイスであって、
前記光変調組成物が、
第１の酸化性化合物であって、請求項１に記載の酸化性化合物である第１の酸化性化合物と、
還元性化合物と、
電解質と、
溶媒と、
を含む、光変調デバイス。
その表面上に第２の透明導電層を備えた第２の透明基板を含み、前記第１の透明導電層および前記第２の透明導電層を互いに対面するように配置することにより設けられた一対の電極と、
前記第１および第２の透明導電層の間に挿入されてセルを形成する絶縁ユニットと、
前記セル中に充填された光変調組成物と、
を含む光変調デバイスであって、
前記光変調組成物が、
第１の酸化性化合物であって、請求項１に記載の酸化性化合物である第１の酸化性化合物と、
還元性化合物と、
電解質と、
溶媒と、
を含む、光変調デバイス。
【発明の詳細な説明】
【技術分野】
【0001】
関連出願の相互参照本出願は、２０１５年１１月２０日に出願された台湾特許出願第１０４１３８４３２号の優先権を主張し、その全体が参照することにより本明細書において援用される。
【0002】
本開示は、有機化合物、光変調組成物、およびそれを用いる光変調デバイスに関する。
【背景技術】
【0003】
光変調デバイスは、それらの低駆動電圧および双安定性により、グリーンエネルギー産業において魅力がある。近年、より長い寿命および耐久性のために、光変調材料の大部分は無機酸化物となっているが、それらの膜は真空蒸着、噴霧熱分解、またはスパッタリングのような高価なプロセスおよび設備を用いて作製される。たとえプロセスのコストを無視したとしても、無機酸化物は依然として、遅いエレクトロクロミックレート、より少ない色のバリエーション（ｃｏｌｏｒ ｖａｒｉａｔｉｏｎ）などのような欠点を有する。有機系において、光変調有機材料は、より多い色のバリエーションおよび速いエレクトロクロミックレートを有する共役系ポリマーを用いる。しかしながら、共役系化合物は、高価なモノマー、複雑な合成、および電解重合による形成、のような欠点を有している。エレクトロクロミック共役系ポリマーは、その共役長（ｃｏｎｊｕｇａｔｅｄ ｌｅｎｇｔｈ）のために、深色（ｄｅｅｐ ｃｏｌｏｒ）を呈する。深色は、電圧を印加することによって明るくなり得るが、共役系ポリマーは完全に透明にはなり得ない。換言すると、共役系ポリマーは、透明状態を生じさせるために電力が供給されなければならず、これにより高い消費エネルギーの問題が生じる。
【0004】
したがって、透明性、膜安定化能（ｆｉｌｍ−ｆｉｒｍｉｎｇ ａｂｉｌｉｔｙ）、およびエレクトロクロミック性の要求を満たす新規なエレクトロクロミック有機材料が必要である。
【先行技術文献】
【特許文献】
【0005】
【特許文献1】米国特許出願公開第２００９０２３１６６３号明細書
【発明の概要】
【発明が解決しようとする課題】
【0006】
共役系化合物は、高価なモノマー、複雑な合成、および電解重合による形成、のような欠点を有している。エレクトロクロミック共役系ポリマーは、その共役長（ｃｏｎｊｕｇａｔｅｄ ｌｅｎｇｔｈ）のために、深色（ｄｅｅｐ ｃｏｌｏｒ）を呈する。深色は、電圧を印加することによって薄くなり得るが、共役系ポリマーは完全に透明になり得ない。換言すると、共役系ポリマーは、透明状態を生じさせるために電力が供給されなければならず、これにより高い消費エネルギーの問題が生じる。
【課題を解決するための手段】
【0007】
本開示は、有機化合物、光変調組成物、およびそれを用いる光変調デバイスに関する。
【0008】
本開示の一実施形態によれば、有機化合物が提供される。有機化合物は、式（Ｉ）で表される化学構造を有する。
【0009】
【化1】
【0010】
式中、Ｘは、
【0011】
【化2】
【0012】
【化3】
【0013】
【化4】
【0014】
【化5】
【0015】
【化6】
または
【0016】
【化7】
である。
【0017】
Ｒ１はアルキルであり、Ｒ３はＨ、アルキル、またはアルコキシであり、Ｒ４はＨまたはメチルである。
【0018】
Ａｒは、
【0019】
【化8】
または
【0020】
【化9】
である。
【0021】
Ａｒ’は
【0022】
【化10】
【0023】
【化11】
【0024】
【化12】
【0025】
【化13】
【0026】
【化14】
または
【0027】
【化15】
である。
【0028】
Ａｒ”は、
【0029】
【化16】
【0030】
【化17】
または
【0031】
【化18】
である。
【0032】
Ａｒ３は、
【0033】
【化19】
【0034】
【化20】
【0035】
【化21】
【0036】
【化22】
【0037】
【化23】
または
【0038】
【化24】
である。
【0039】
Ｒ２はＨ、アルキルまたはアルコキシである。
【0040】
本開示の別の実施形態によれば、光変調組成物が提供される。組成物は、第１の酸化性化合物（ｏｘｉｄｉｚａｂｌｅ ｃｏｍｐｏｕｎｄ）、還元性化合物（ｒｅｄｕｃｉｂｌｅ ｃｏｍｐｏｕｎｄ）、電解質および溶媒を含み、このうち第１の酸化性化合物は上記有機化合物を含む。
【0041】
本開示の別の実施形態によれば、光変調デバイスが提供される。光変調デバイスは、一対の電極、絶縁ユニット、および光変調組成物を含む。 一対の電極は、その表面上に第１の透明導電層を備える第１の透明基板と、その表面上に第２の透明導電層を備える第２の透明基板とを含む。 一対の電極は、第１の透明導電層と第２の透明導電層とを互いに対面するよう配置することにより、設けられる。絶縁ユニットは、第１および第２の透明導電層間に挿入されて、セルを形成する。そして、光変調組成物がセル中に充填される。組成物は、第１の酸化性化合物、還元性化合物、電解質、および溶媒を含む。第１の酸化性化合物は、上述した有機化合物を含む。
【発明の効果】
【0042】
光変調デバイスは、適した電圧が印加された後に、無色から特定の色（例えば、黄緑色、空色、青色、藍色（ｄｅｅｐ ｂｌｕｅ）、または濃い紫色（ｄｅｅｐ ｐｕｒｐｌｅ））に変化し得る。特定の色および電圧は、光変調組成物の有機酸化性化合物の化学構造によって決まる。電圧がオフになると、１分以内にセルの内容物が再び完全に退色する（ｂｌｅａｃｈ）。１００００の着色（ｃｏｌｏｒｉｎｇ）／退色（ｂｌｅａｃｈｉｎｇ）サイクルを経た後でも、セルは依然としてよく機能する。つまり、光変調組成物溶液は良好な安定性を備える。
【図面の簡単な説明】
【0043】
添付の図面を参照しながら、以下の実施形態において詳細な説明を行う。
【0044】
添付の図面を参照しながら後続の詳細な説明および実施例を読むことによって、本発明をより十分に理解することができる。【図1】本開示の一実施形態における光変調デバイスを示している。
【図2】本開示の実施例における有機化合物のサイクリックボルタンメトリー図を示している。
【図3】本開示の実施例における有機化合物のサイクリックボルタンメトリー図を示している。
【図4】本開示の実施例における有機化合物のニュートラルおよび酸化状態の透過スペクトルを示している。
【図5】本開示の実施例における有機化合物のニュートラルおよび酸化状態の透過スペクトルを示している。
【図6】本開示の実施例における光変調デバイスのニュートラルおよび酸化状態の透過スペクトルを示している。
【図7】本開示の実施例におけるスイッチングサイクル後の光変調デバイスの透過スペクトルを示している。
【図8】本開示の実施例における光変調デバイスにそれぞれ異なる電圧を印加した後の透過スペクトルを示している。
【発明を実施するための形態】
【0045】
本開示のいくつかの実施形態によれば、有機化合物が提供される。当該有機化合物は、式（Ｉ）で示される化学構造を有する。
【0046】
【化25】
【0047】
式中、Ｘは、
【0048】
【化26】
【0049】
【化27】
【0050】
【化28】
【0051】
【化29】
【0052】
【化30】
または
【0053】
【化31】
であってよい。
【0054】
Ｒ１はアルキルであってよく、Ｒ３はＨ、アルキル、またはアルコキシであってよく、Ｒ４はＨまたはメチルであってよい。Ａｒは、
【0055】
【化32】
または
【0056】
【化33】
であってよい。
【0057】
Ａｒ’は、
【0058】
【化34】
【0059】
【化35】
【0060】
【化36】
【0061】
【化37】
【0062】
【化38】
または
【0063】
【化39】
である。
【0064】
Ａｒ”は、
【0065】
【化40】
【0066】
【化41】
または
【0067】
【化42】
である。
【0068】
Ａｒ３は、
【0069】
【化43】
【0070】
【化44】
【0071】
【化45】
【0072】
【化46】
【0073】
【化47】
または
【0074】
【化48】
である。
【0075】
Ｒ２はＨ、アルキルまたはアルコキシであり得る。
【0076】
一実施形態において、Ｒ１はＣ１−８アルキル基であり得る。
【0077】
一実施形態において、Ｒ１はＣ１−４アルキル基であり得る。
【0078】
一実施形態において、Ｒ２は水素、Ｃ１−８アルキル基、またはＣ１−８アルコキシ基であり得る。
【0079】
一実施形態において、Ｒ２はＣ１−４アルキル基、またはＣ１−４アルコキシ基であり得る。
【0080】
一実施形態において、Ｒ３は水素、Ｃ１−８アルキル基、またはＣ１−８アルコキシ基であり得る。
【0081】
一実施形態において、Ｒ３はＣ１−４アルキル基、またはＣ１−４アルコキシ基であり得る。
【0082】
有機化合物は、カルボン酸とジアミンとの反応から調製され得る。ジアミンの中間生成物、ジニトロは、文献の方法にしたがって調製され得、そして以下の式２または３に示される還元によりジニトロからジアミンが得られる（Ｊ． Ｐｏｌｙｍ． Ｓｃｉ． Ｐａｒｔ Ａ： Ｐｏｌｙｍ． Ｃｈｅｍ． ２００６， ４４， ｐｐ４５７９−４５９２、その開示全体が参照することにより本明細書に取り込まれる）。式２および３におけるＡｒ’、Ａｒ”、およびＲ２は、上記式（１）において定義されたのと同じ意味を持つ。上記有機化合物は、エレクトロクロミック素子、半導体、太陽電池、有機エレクトロルミネッセンス素子、非線形材料の活性物質（ａｃｔｉｖｅ ｓｕｂｓｔａｎｃｅ）などとして適用可能である。
【0083】
【化49】
【0084】
【化50】
【0085】
本開示のいくつかの実施形態によれば、本開示は、次式で表される構造を有する有機化合物も提供する。
【0086】
【化51】
【0087】
式中、Ｒ５はＣ１−８アルキル基であり得る。
【0088】
本開示のいくつかの実施形態によれば、本開示は、次式で表される構造を有する有機化合物も提供する。
【0089】
【化52】
【0090】
式中、Ｒ４はＣ１−８アルキル基であり得る。
【0091】
本開示のいくつかの実施形態によれば、本開示は、次式で表される構造を有する有機化合物も提供する。
【0092】
【化53】
【0093】
式中、Ｒ６はＣ１−８アルキル基であり得る。
【0094】
本開示のいくつかの実施形態によれば、本開示は、次式で表される構造を有する有機化合物も提供する。
【0095】
【化54】
【0096】
式中、Ｒ４はＣ１−８アルキル基であり得る。
【0097】
本開示の一実施形態によれば、上述した有機化合物は、還元性化合物、電解質および溶媒と組み合わせて、光変調組成物を形成することができる第１の酸化性化合物として用いられ得る。一実施形態において、酸化性化合物と電解質とのモル比は１：１から１：２０であり、還元性化合物と電解質とのモル比は１：１から１：２０である。
【0098】
いくつかの実施形態において、電解質は、少なくとも１つの不活性伝導塩（ｉｎｅｒｔ ｃｏｎｄｕｃｔｉｎｇ ｓａｌｔ）を含み得る。適した不活性伝導塩の例には、リチウム塩、ナトリウム塩、およびテトラアルキルアンモニウム塩、例えばテトラブチルアンモニウムが含まれる。適した溶媒には、選択された電圧でレドックス不活性（ｒｅｄｏｘ−ｉｎｅｒｔ）であり、かつ分解して求電子剤（ｅｌｅｃｔｒｏｐｈｉｌｅｓ）もしくは求核試薬（ｎｕｃｌｅｏｐｈｉｌｅｓ）を形成し得ない、またはそれ自体十分に強力な求電子剤もしくは求核試薬として反応し得ないため、着色されたイオン性フリーラジカル（ｉｏｎｉｃ ｆｒｅｅ ｒａｄｉｃａｌｓ）と反応し得ない溶媒が含まれる。適した溶媒の例には、プロピレンカーボネート（ＰＣ）、ガンマ−ブチロラクトン（ＧＢＬ，γ−ｂｕｔｙｒｏｌａｃｔｏｎｅ）、アセトニトリル、プロピオニトリル、グルタロニトリル、メチルグルタロニトリル、３，３’−オキシジプロピオニトリル、ヒドロキシプロピオニトリル、ジメチルホルムアミド、Ｎ−メチルピロリドン、スルホラン、３−メチルスルホラン、またはこれらの混合物が含まれる。電解質の濃度は０．０１Ｍから１．５Ｍの間とすることができる。
【0099】
いくつかの実施形態において、還元性化合物は、
【0100】
【化55】
【0101】
【化56】
および
【0102】
【化57】
からなる群から選ばれ得る。
【0103】
本開示のいくつかの実施形態において、酸化性化合物は第２の酸化性化合物を含んでいてよく、それは、
【0104】
【化58】
【0105】
【化59】
【0106】
【化60】
【0107】
【化61】
【0108】
【化62】
またはこれらの組み合わせであってよい。
【0109】
式中、Ｒ８はＨまたはアルキル基である。
【0110】
本開示のいくつかの実施形態によれば、光変調デバイスが提供され得る。図１に示されるように、光変調デバイスは、一対の電極、絶縁ユニット、および光変調組成物を含む。一対の電極１２、１８は、その表面上に第１の透明導電層１３を備える第１の透明基板１１、およびその表面上に第２の透明導電層１７を備える第２の透明基板１９を含む。一対の電極１２、１８は、第１の透明導電層１３と第２の透明導電層１７とを互いに対面させるように配することにより設置される。絶縁ユニット１４が第１および第２の透明導電層１３、１７間に挿入されると共にシールされて、セル１５が形成される。そして、絶縁ユニット１４上のポート（ｐｏｒｔ）（図示せず）から、上述の光変調組成物がセル１５内へ導入される。光変調デバイス１０が形成されるようポートがシールされる。
【0111】
本開示のいくつかの実施形態において、透明基板はガラス、またはポリカーボネートのようなプラスチックからなるものとしてよい。導電層は、酸化インジウムスズ（ＩＴＯ）、アンチモン−もしくはフッ素−ドープ酸化スズ、アンチモン−もしくはアルミニウムドープ酸化亜鉛、酸化スズ、または、例えば、任意で置換されてもよい、ポリチエニル類（ｐｏｌｙｔｈｉｅｎｙｌｓ）、ポリピロール類（ｐｏｌｙｐｙｒｒｏｌｅｓ）、ポリアニリン類（ｐｏｌｙａｎｉｌｉｎｅｓ）、ポリアセチレン（ｐｏｌｙａｃｅｔｙｌｅｎｅ）のような導電有機ポリマーからなるものとしてよい。
【0112】
本開示のいくつかの実施形態において、絶縁ユニットは、スペーサエレメントを、熱硬化性または光化学硬化性（ｐｈｏｔｏｃｈｅｍｉｃａｌｌｙ ｃｕｒａｂｌｅ）接着剤とブレンドすることによって形成され得る。スペーサーエレメントは、プラスチックもしくはガラスの小球体または特定の砂分（ｓａｎｄ ｆｒａｃｔｉｏｎｓ）であってよい。
【0113】
本開示のいくつかの実施形態において、第１の導電材料層から第２の導電材料層までの距離は１０μｍから２００μｍの間とすることができる。
【0114】
光変調デバイスは、適した電圧が印加されると、無色から、特定の色(例えば、黄緑色、空色、青色、藍色、または濃い紫色)に変化し得る。特定の色および電圧は、光変調組成物の有機酸化性化合物の化学構造によって決まる。電圧がオフになった後、セルの内容物は１分以内に再び完全に脱色する（ｂｌｅａｃｈ）。下記の実験は、１００００の着色／脱色サイクルを経た後も、セルが依然として十分に機能したことを示している。つまり、光変調組成物溶液は良好な安定性を備える。
【0115】
以下に、当該分野において通常の知識を有する者が容易に理解できるよう、添付の図面を参照しながら、例示的な実施形態を詳細に記載する。本発明概念は、本明細書に述べられた例示的な実施形態に限定されることなく、様々な形で具体化され得る。明確とするために既知の部分についての記述は省いており、全体にわたり類似する参照数字は類似する構成要素に言及する。
【実施例】
【0116】
以下の実施例では、ＣＨ Ｉｎｓｔｒｕｍｅｎｔｓ６１２Ｃで電気化学分析を行って、薄膜の電位を走査した。サイクリックボルタンメトリー（ＣＶ）を三電極系により行った。このうち、ＩＴＯガラス（被覆ポリマー（ｃｏａｔｅｄ ｐｏｌｙｍｅｒ）の面積は約２．０ｃｍ×０．８ｃｍ）を作用電極として用い、Ａｇ／ＡｇＣｌ電極（飽和ＫＣｌ溶液中）を参照電極として用い、白金線を補助電極として用い、０．１Ｍのテトラブチルアンモニウム過塩化物（ｔｅｔｒａｂｕｔｙｌａｍｍｏｎｉｕｍ ｐｅｒｃｈｌｏｒｉｄｅ）溶液（アセトニトリル中）を電解質として用い、かつ走査速度を５０ｍＶ／ｓとした。酸化還元電位の平均値を半波電位として定義した。
【0117】
実施例Ａ１：有機化合物（Ａ１）の調製
【0118】
４−メトキシトリフェニルアミン系ジアミン（化合物（Ｉ））１０．０ｇおよびイソ酪酸（化合物（ＩＩ））６．４ｇを反応フラスコ中で混合した。溶媒としてのジメチルアセトアミド（ＤＭＡｃ）２５ｍｌをその反応フラスコに加え、次いで、触媒としてのリン酸トリフェニル（ＴＰＰ）２０．３ｇおよびピリジン５．６８ｇをその反応フラスコに加えた。その反応フラスコ中の混合物を１０５℃、４時間加熱してから、室温まで冷却させた。その冷却した反応混合物をエタノール中に注ぎ入れ、固体を沈澱させてから、ろ過してその固体を回収した。その固体を水で洗浄してから乾燥させて、化合物（Ａ１）（白色の固体）を得た。上記反応の合成経路は次のようであった。
【0119】
【化63】
【0120】
化合物（Ａ１）の物理測定の結果を以下に記す：１Ｈ ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１．０２（ｄ，Ｊ＝７．０Ｈｚ，６Ｈ），２．４９（ｍ，２Ｈ），３．６６（ｓ，３Ｈ），６．７８（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），６．８１（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），６．８７（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．４１（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），９．６５（ｓ，２Ｈ）．１３Ｃ ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１９．５，３４．８，５５．２，１１４．８，１２０．４，１２２．９，１２５．７，１３３．９，１４０．５，１４３．０，１５５．２，１７４．８．Ａｎａｌ．ｃａｌｃｄ ｆｏｒ Ｃ２７Ｈ３１Ｎ３Ｏ３：Ｃ，７２．７８；Ｈ，７．０１；Ｎ，９．４３；ｆｏｕｎｄ：Ｃ，７２．６９；Ｈ，７．０３；Ｎ，９．５１．
【0121】
化合物（Ａ１）は、図２に示されるサイクリックボルタンメトリーＣＶ図、以下の表１に示される酸化還元電位、図４に示されるニュートラルおよび酸化状態の透過スペクトル、ならびに以下の表２に示される異なる波長におけるニュートラルおよび酸化状態の透過率を有する。
【0122】
実施例Ａ２：有機化合物（Ａ２）の調製
【0123】
４−メトキシトリフェニルアミン系ジアミン（化合物（Ｉ））１０．０ｇおよびシクロヘキサン酸（ｃｙｃｌｏｈｅｘａｎｏｉｃ ａｃｉｄ）（化合物（ＩＩＩ））８．４ｇを反応フラスコ中で混合した。溶媒としてのジメチルアセトアミド（ＤＭＡｃ）２５ｍｌをその反応フラスコに加え、次いで、触媒としてのリン酸トリフェニル（ＴＰＰ）２０．３ｇおよびピリジン５．６８ｇをその反応フラスコに加えた。その反応フラスコ中の混合物を１０５℃、４時間加熱してから、室温まで冷却させた。その冷却した反応混合物をエタノール中に注ぎ入れ、固体を沈澱させてから、ろ過してその固体を回収した。その固体を水で洗浄してから乾燥させて、化合物（Ａ２）（白色の固体）を得た。上記反応の合成経路は次のようであった。
【0124】
【化64】
【0125】
化合物（Ａ２）の物理測定の結果を以下に記す：１Ｈ ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１．１３〜１．４４（ｍ，１０Ｈ），１．６３〜１．７９（ｍ，１０Ｈ），２．２９（ｔ，２Ｈ），３．７２（ｓ，３Ｈ），６．８４（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），６．８８（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），６．９５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．４８（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），９．６７（ｓ，２Ｈ）．１３Ｃ ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１３．９，２２．０，２５．１，２８．５，２８．６，３１．２，５５．２，１１４．８，１２０．２，１２２．８，１２５．８，１４０．５，１４３．０，１５５．２４，１７０．８． Ａｎａｌ． ｃａｌｃｄ ｆｏｒ Ｃ３３Ｈ３９Ｎ３Ｏ３：Ｃ，７５．４；Ｈ，７．４８；Ｎ，７．９９；ｆｏｕｎｄ：Ｃ，７４．８；Ｈ，７．４５；Ｎ，７．８７．
【0126】
化合物（Ａ２）は、以下の表１に示される酸化還元電位、以下の表２に示される異なる波長におけるニュートラルおよび酸化状態の透過率を有する。
【0127】
実施例Ａ３：有機化合物（Ａ３）の調製
【0128】
４−メトキシトリフェニルアミン系ジアミン（化合物（Ｉ））１０．０ｇおよびオクタン酸（化合物（ＩＶ））９．４５ｇを反応フラスコ中で混合した。溶媒としてのジメチルアセトアミド（ＤＭＡｃ）２５ｍｌをその反応フラスコに加え、次いで、触媒としてのリン酸トリフェニル（ＴＰＰ）２０．３ｇおよびピリジン５．６８ｇをその反応フラスコに加えた。その反応フラスコ中の混合物を１０５℃、４時間加熱してから、室温まで冷却させた。その冷却した反応混合物をエタノール中に注ぎ入れ、固体を沈澱させてから、ろ過してその固体を回収した。その固体を水で洗浄してから乾燥させて、化合物（Ａ３）（白色の固体）を得た。上記反応の合成経路は次のようであった。
【0129】
【化65】
【0130】
化合物（Ａ３）の物理測定の結果を以下に記す：１Ｈ ＮＭＲ（５００ ＭＨｚ，ＤＭＳＯ−ｄ６）：δ０．８６（ｔ，６Ｈ），１．２６〜１．５９（ｍ，１６Ｈ），２．５１（ｔ，４Ｈ），３．７３（ｓ，３Ｈ），６．８５（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），６．８８（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），６．９５（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．４７（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），９．７６（ｓ，２Ｈ）．１３Ｃ ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１３．９，２２．０，２５．２，２８．５，２８．６，３１．２，５５．２，１１４．８，１２０．２，１２２．８，１２５．８，１３３．８，１４０．５，１４３．０，１５５．２，１７０．８． Ａｎａｌ． ｃａｌｃｄ ｆｏｒ Ｃ３３Ｈ４３Ｎ３Ｏ３：Ｃ，７４．８２；Ｈ，８．１８；Ｎ，７．９３；ｆｏｕｎｄ：Ｃ，７４．８９；Ｈ，８．０９；Ｎ，７．８８．
【0131】
化合物（Ａ３）は、以下の表１に示される酸化還元電位、以下の表２に示される異なる波長におけるニュートラルおよび酸化状態の透過率を有する。
【0132】
実施例Ａ４：有機化合物（Ａ４）の調製
【0133】
４−メトキシペンタフェニルアミン系ジアミン（化合物（Ｖ））１０．０ｇおよびシクロヘキサン酸（化合物（ＩＩＩ））５．１ｇを反応フラスコ中で混合した。溶媒としてのジメチルアセトアミド（ＤＭＡｃ）２５ｍｌをその反応フラスコに加え、次いで、触媒としてのリン酸トリフェニル（ＴＰＰ）２０．３ｇおよびピリジン５．６８ｇをその反応フラスコに加えた。その反応フラスコ中の混合物を１０５℃、４時間加熱してから、室温まで冷却させた。その冷却した反応混合物をエタノール中に注ぎ入れ、固体を沈澱させてから、ろ過してその固体を回収した。その固体を水で洗浄してから乾燥させて、化合物（Ａ４）（白色の固体）を得た。上記反応の合成経路は次のようであった。
【0134】
【化66】
【0135】
化合物（Ａ４）の物理測定の結果を以下に記す：１Ｈ ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１．２４〜１．３８（ｍ，１０Ｈ），１．４０〜１．７５（ｍ，１０Ｈ），１．７７（ｔ，２Ｈ），３．７２（ｓ，６Ｈ），６．７９（ｓ，４Ｈ），６．８７〜６．８８（ｍ，６Ｈ），６．９７（ｄ，Ｊ＝８．５Ｈｚ，２Ｈ），７．４７（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），９．６９（ｓ，２Ｈ）．１３Ｃ ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ６）：δ２５．２，２５．４，２９．１，４４．７，５５．２，１１４．８，１２０．３，１２３．０，１２３．２，１２５．９，１３４．０，１４０．４，１４２．０，１４２．９，１５５．３，１７３．８．Ａｎａｌ． ｃａｌｃｄ ｆｏｒ Ｃ４６Ｈ５２Ｎ４Ｏ４：Ｃ，７６．２１；Ｈ，７．２３；Ｎ，７．７３；ｆｏｕｎｄ：Ｃ，７５．９５；Ｈ，７．２９；Ｎ，７．７５．
【0136】
化合物（Ａ４）は、図３に示されるサイクリックボルタンメトリーＣＶ図、以下の表１に示される酸化還元電位、図５に示されるニュートラルおよび酸化状態の透過スペクトル、ならびに以下の表２に示される異なる波長におけるニュートラルおよび酸化状態の透過率を有する。
【0137】
実施例Ｂ１：有機化合物（Ｂ１）の調製
【0138】
４−メトキシトリフェニルアミン系ジアミン（化合物（Ｉ））１．５０ｇおよびヘキサヒドロフタル酸無水物（化合物（ＶＩ））１．７０ｇを反応フラスコ中で混合した。溶媒としてのジメチルアセトアミド（ＤＭＡｃ）２．５ｍｌをその反応フラスコに加え、次いで、触媒としての少量のイソキノリンをその反応フラスコに加えた。その反応フラスコ中の混合物を２１０℃、５時間加熱してから、室温まで冷却させた。その冷却した反応混合物をメタノールで希釈し、水中に注ぎ入れ、固体を沈澱させてから、ろ過してその固体を回収した。その固体を水で洗浄してから乾燥させて、化合物（Ｂ１）（ベージュ色の固体）を得た。上記反応の合成経路は次のようであった。
【0139】
【化67】
【0140】
化合物（Ｂ１）の物理測定の結果を以下に記す：１Ｈ ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１．３８（ｍ，４Ｈ），１．７３（ｑ，４Ｈ），３．０８（ｑ，２Ｈ），３．７５（ｓ，３Ｈ），６．９７（ｄ，Ｊ＝９．５Ｈｚ，２Ｈ），７．０２（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ），７．１１（ｄ，Ｊ＝９．５Ｈｚ，２Ｈ），７．１４（ｄ，Ｊ＝９．０Ｈｚ，４Ｈ）．１３Ｃ ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ６）：δ２１．４，２３．４，５５．３，１１５．４，１２２．０，１２６．２，１２７．９，１２８．１，１３９．１，１４７．０，１５６．７，１７８．８． Ａｎａｌ． ｃａｌｃｄ ｆｏｒ Ｃ３５Ｈ３５Ｎ３Ｏ５：Ｃ，７２．７７；Ｈ，６．１１；Ｎ，７．２７；ｆｏｕｎｄ：Ｃ，７２．３５；Ｈ，６．１６；Ｎ，７．２５．
【0141】
化合物（Ｂ１）は、図２に示されるサイクリックボルタンメトリーＣＶ図、以下の表１に示される酸化還元電位、図４に示されるニュートラルおよび酸化状態の透過スペクトル、ならびに以下の表２に示される異なる波長におけるニュートラルおよび酸化状態の透過率を有する。
【0142】
実施例Ｂ２：有機化合物（Ｂ２）の調製
【0143】
４−メトキシペンタフェニルアミン系ジアミン（化合物（Ｖ））５．０ｇおよびヘキサヒドロフタル酸無水物（化合物（ＶＩ））３．０６ｇを反応フラスコ中で混合した。溶媒としてのジメチルアセトアミド（ＤＭＡｃ）７．５ｍｌをその反応フラスコに加え、次いで、触媒としての少量のイソキノリンをその反応フラスコに加えた。その反応フラスコ中の混合物を２１０℃、５時間加熱してから、室温まで冷却させた。その冷却した反応混合物をメタノールで希釈し、水中に注ぎ入れ、固体を沈澱させてから、ろ過してその固体を回収した。その固体を水で洗浄してから乾燥させて、化合物（Ｂ２）（ベージュ色の固体）を得た。上記反応の合成経路は次のようであった。
【0144】
【化68】
【0145】
化合物（Ｂ２）の物理測定の結果を以下に記す：１Ｈ ＮＭＲ（５００ＭＨｚ，ＤＭＳＯ−ｄ６）：δ１．３６〜１．４２（ｍ，８Ｈ），１．７０〜２．００（ｍ，８Ｈ），３．０８（ｔ，４Ｈ），３．７４（ｓ，６Ｈ），６．９２〜７．１０（ｍ，２０Ｈ）．１３Ｃ ＮＭＲ（１２５ＭＨｚ，ＤＭＳＯ−ｄ６）：δ２１．３，２１．４，２３．３，５５．２，１１５．２，１２０．２，１２４．９，１２５．０，１２７．５，１２７．７，１３９．４，１４２．２，１４７．６，１５６．３，１７８．８． Ａｎａｌ． ｃａｌｃｄ ｆｏｒ Ｃ４８Ｈ４６Ｎ４Ｏ６：Ｃ，７４．４０；Ｈ，５．９８；Ｎ，７．２３；ｆｏｕｎｄ：Ｃ，７４．２１；Ｈ，６．０３；Ｎ，７．２７．
【0146】
化合物（Ｂ２）は、図３に示されるサイクリックボルタンメトリーＣＶ図、以下の表１に示される酸化還元電位、図５に示されるニュートラルおよび酸化状態の透過スペクトル、ならびに以下の表２に示される異なる波長におけるニュートラルおよび酸化状態の透過率を有する。
【0147】
【表1】
【0148】
表１ならびに図２および図３は、トリフェニルアミン系（化合物Ａ１〜Ａ３およびＢ１）が１つの酸化還元ピークのみを有し、ペンタフェニルジアミン系（化合物Ａ４およびＢ２）が２つの酸化還元ピークを有していたことを示している。アミド基（ａｍｉｄｏ ｇｒｏｕｐ）とイミド基（ｉｍｉｄｏ ｇｒｏｕｐ）間の電位ピークの差は大きかった（Ａ１ ｖｓ．Ｂ１、およびＡ４ ｖｓ．Ｂ２）。異なる末端官能基を用いることにより、有機化合物の酸化還元電位を調整することができる。
【0149】
【表2】
【0150】
表２、図４は、可視領域において、トリフェニルアミン系（化合物Ａ１およびＢ１）の遮蔽効果がＰＳＮの遮蔽効果よりも良好であったことを示している。ペンタフェニルジアミン系は可視領域に吸収を持ち、かつＮＩＲ領域における熱線吸収が良好であった。言い換えると、ペンタフェニルジアミン系化合物は、抗紫外線活性（ａｎｔｉ−ｕｌｔｒａｖｉｏｌｅｔ ａｃｔｉｖｉｔｙ）およびＮＩＲ領域における吸収という特性を有していた。
【0151】
実施例Ｃ１：光変調デバイスの作製
【0152】
テトラブチルアンモニウムテトラフルオロボラート（Ｔｅｔｒａｂｕｔｙｌ ａｍｍｏｎｉｕｍ ｔｅｔｒａｆｌｕｏｒｏｂｏｒａｔｅ，ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ａ２およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ａ２の濃度は０．１Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。その光変調デバイスに１．４Ｖの電圧をかけて、以下の表３に示されるように、デバイスの透過率を測定した。
【0153】
実施例Ｃ２：光変調デバイスの作製
【0154】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ｂ１およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ｂ１の濃度は０．１Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。その光変調デバイスに１．６Ｖの電圧をかけて、以下の表３に示されるように、デバイスの透過率を測定した。デバイスのニュートラル状態（オフ状態）および酸化状態（オン状態）の透過スペクトルは図６に示されるようであった。
【0155】
実施例Ｃ３：光変調デバイスの作製
【0156】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ａ４およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ａ４の濃度は０．１Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。その光変調デバイスに１．１Ｖの電圧をかけて、以下の表３に示されるように、デバイスの透過率を測定した。
【0157】
実施例Ｃ４：光変調デバイスの作製
【0158】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ｂ２およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ｂ２の濃度は０．１Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。その光変調デバイスに１．３Ｖの電圧をかけて、以下の表３に示されるように、デバイスの透過率を測定した。
【0159】
【表3】
【0160】
表３および図６は、ビオロゲンを加えた実施例の遮蔽効果が、６００ｎｍあたりの波長で向上したことを示している。４００〜５００ｎｍ付近の波長におけるペンタフェニルジアミン系の実施例Ｃ３およびＣ４の遮蔽効果は、実施例Ｃ１およびＣ２の遮蔽効果よりも大きかった。トリフェニルアミンおよびペンタフェニルジアミン系はより良好な共役特性を有していたため、ＰＳＮと比較して、３５０〜８００ｎｍの範囲内で全ての実施例が遮蔽効果を有していた。
【0161】
実施例Ｄ：光変調デバイスの作製
【0162】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ａ１およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ａ１の濃度は０．１Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。
【0163】
光変調デバイスに１．３Ｖの電圧を３．２５０秒かけ（オン状態）、−１．３Ｖの電圧を０．３７５秒かけ（オフ状態）、次いで０Ｖを３．６７５秒維持した。上の手法を繰り返して、デバイスにサイクル寿命試験を行った。図７の透過スペクトルに示されるように、デバイスは、可視領域において全く吸収がない元のニュートラル状態から、藍色（ｄｅｅｐ ｂｌｕｅ）（酸化状態）に変わった。さらに、１００００のオン／オフサイクル後も、デバイスは依然として機能し、オン／オフの透過スペクトルを有していたため、デバイスは安定している。異なる波長および異なる状態におけるデバイスの透過率は以下の表４に示されるようであった。
【0164】
【表4】
【0165】
実施例Ｅ：透明−緑色相補式（ｃｏｍｐｌｅｍｅｎｔａｒｙ）光変調デバイスの作製
【0166】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ａ１、５，１０−ジメチルフェナジン（５，１０−ｄｉｍｅｔｈｙｌｐｈｅｎａｚｉｎｅ，ＤＭＰ）およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ａ１の濃度は０．０２５Ｍ、ＤＭＰの濃度は０．０２５Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。
【0167】
光変調デバイスに電圧をかけ徐々に１．３Ｖまでにすると、４５０ｎｍの波長においてデバイスの透過率が１０．４％まで低減したことが、そのスペクトルよりわかる。デバイスは、ニュートラル状態における透明から、深緑色（酸化状態）に変わった。さらに、電圧をオフに切り替えた後、１秒内にデバイスは透明（オフ状態）に戻ることができる。
【0168】
実施例Ｆ：透明−藍色（ｄｅｅｐ ｂｌｕｅ）相補式光変調デバイスの作製
【0169】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ａ１、フェノチアジン（ＰＳＮ）、メチルフェノチアジン（ＭｅＰＳＮ）およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ａ１の濃度は０．０５Ｍ、ＰＳＮの濃度は０．０５Ｍ、ＭｅＰＳＮの濃度は０．０５Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。
【0170】
光変調デバイスに電圧をかけ徐々に１．３Ｖまでにすると、４５０ｎｍの波長においてデバイスの透過率が１０．４％まで低減したことが、そのスペクトルよりわかる。デバイスは、ニュートラル状態における透明から、藍色（酸化状態）に変わった。さらに、電圧をオフに切り替えた後、１秒内にデバイスは透明（オフ状態）に戻ることができる。
【0171】
実施例Ｇ:透明−濃黒色（ｄａｒｋ）相補式光変調デバイスの作製
【0172】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、化合物Ａ１、フェノチアジン（ＰＳＮ）、メチルフェノチアジン（ＭｅＰＳＮ）およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし化合物Ａ１の濃度は０．１Ｍ、ＰＳＮの濃度は０．１Ｍ、ＭｅＰＳＮの濃度は０．１Ｍ、ビオロゲンの濃度は０．１Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。
【0173】
光変調デバイスに電圧をかけ徐々に１．３Ｖまでにすると、４５０ｎｍの波長においてデバイスの透過率が１０．４％まで低減したことが、そのスペクトルよりわかる。デバイスは、ニュートラル状態における透明から、濃い黒色（酸化状態）に変わった。異なる波長および異なる状態におけるデバイスの透過スペクトルは図８に示すとおりであった。さらに、電圧をオフに切り替えた後、１秒内にデバイスは透明（オフ状態）に戻ることができる。
【0174】
比較例Ｈ：光変調デバイスの作製
【0175】
テトラブチルアンモニウムテトラフルオロボラート（ＴＢＡＢＦ４）をプロピレンカーボネート（ＰＣ）中に溶解し、０．５Ｍ溶液を作った。次に、フェノチアジン（ＰＳＮ）およびビオロゲン［（ＨＶ（ＢＦ４）２］を上記溶液中に溶解して、光変調組成物溶液を作った。ただし、ＰＳＮの濃度は０．１Ｍ、ビオロゲンの濃度は０．０５Ｍとした。２枚のＩＴＯ導電ガラスプレートを所望のサイズにカットし、プレートのＩＴＯ層を互いに対面させた。絶縁ユニットを２枚のＩＴＯ導電ガラスプレートに接続してセルを作った。絶縁ユニット上のポートから、上述の光変調組成物をセル中に導き、セルが光変調組成物溶液で満たされるようにした。光変調デバイスが形成されるようポートをシールした。ガラスプレート間の距離は約５０μｍとした。そのニュートラルおよび酸化状態の透過スペクトルを図４に示し、かつ異なる波長におけるニュートラルおよび酸化状態の透過率を表２に示した。
【0176】
光変調デバイスに電圧をかけ徐々に１．３Ｖまでにすると、デバイスは、ニュートラル状態における透明から、藍色（酸化状態）に変わった。異なる波長および異なる状態におけるデバイスの透過スペクトルは図６に示すとおりであった。異なる波長におけるデバイスの透過率を表３に示した。
【0177】
当業者には、開示した実施形態に各種修飾および変化を加え得るということが明らかであろう。明細書および実施例は単に例示として見なされるように意図されており、本開示の真の範囲は、以下の特許請求の範囲およびそれらの均等物によって示される。
【符号の説明】
【0178】
１０…光変調デバイス１２、１８…一対の電極
１１…第１の透明基板
１３…第１の透明導電層
１９…第２の透明基板
１７…第２の透明導電層
１４…絶縁ユニット
１５…セル
【外国語明細書】
Organic Compounds, light modulating Composition and light modulating devices employing the same
Cross reference to related Applications
[0001] This Application claims priority of Taiwan Patent Application No.104138432, filed on November 20, 2015, the entirety of which is incorporated by reference herein.
Technical Field
[0002] The present disclosure relates to organic compounds, light modulating compositions, and light modulating devices employing the same.
Background
[0003] Light modulating devices are attractive in green energy industries due to their low driving voltage and bistability. Recently, the major part of light modulating material is inorganic oxides for longer lifetime and endurance, however, films thereof are prepared by using expensive processes and equipment such as vacuum deposition, spray pyrolysis, or sputtering. Even ignoring the cost of processing, the inorganic oxide still has shortcomings such as a slow electrochromic rate, less color variation, and the like. In an organic system, light modulating organic materials use conjugated polymer with more color variation and fast electrochromic rates. However, the conjugated compound has shortcomings such as expensive monomers, complicated synthesis, and formation by electro-polymerization. The electrochromic conjugated polymer has an appearance of deep color due to its conjugated length. Although the deep color can be lightened by applying a voltage, the conjugated polymer cannot be fully transparent. In other words, the conjugated polymer must be electrified to effect a transparent state, thereby leading to the problem of high energy consumption.
[0004] Accordingly, there is a need for a novel electrochromic organic material to meet the requirements of transparency, film-firming ability, and electrochromicity.
[0005] Patent Document: U.S. Pub. No. 20090231663.
Disclosure of the invention
[0006] Problems to be solved
[0007] The conjugated compound has shortcomings such as expensive monomers, complicated synthesis, and formation by electro-polymerization. The electrochromic conjugated polymer has an appearance of deep color due to its conjugated length. Although the deep color can be lightened by applying a voltage, the conjugated polymer cannot be fully transparent. In other words, the conjugated polymer must be electrified to effect a transparent state, thereby leading to the problem of high energy consumption.
[0008] Means for solving the problems
[0009] The present disclosure relates to organic compounds, light modulating compositions, and light modulating devices employing the same.
[0010] In accordance with one embodiment of the disclosure, an organic compound is provided. The organic compound has a chemical structure represented by formula (I):
X-Ar-X (I)
wherein
[0011] In accordance with another embodiment of the disclosure, a light modulating composition is provided. The composition includes a first oxidizable compound, a reducible compound, an electrolyte and a solvent, wherein the first oxidizable compound includes the aforementioned organic compound.
[0012] In accordance with another embodiment of the disclosure, a light modulating device is provided. The light modulating device includes a pair of electrodes, an isolating unit and a light modulating composition. The pair of electrodes includes a first transparent substrate with a first transparent conductive layer on a surface of the transparent substrate and a second transparent substrate with a second transparent conductive layer on a surface of the transparent substrate. The pair of electrodes is disposed by arranging the first transparent conductive layer and the second transparent conductive layer to face each other. The isolating unit inserted between the first and second transparent conductive layers to form a cell. Then, the light modulating composition is filled in the cell. The composition includes a first oxidizable compound, a reducible compound, an electrolyte and a solvent. The first oxidizable compound includes the aforementioned organic compounds.
[0013] Effect of the invention
[0014] The light modulating device will change from colorless to a specific color (e.g. yellow green, sky blue, blue, deep blue, or deep purple) after being applied with a suitable voltage. The specific color and the voltage depend on the chemical structure of the organic oxidizable compound of the light modulating composition. After the voltage is switched off, the cell contents completely bleach once more within 1 min. The cell still work well after operating 10,000 coloring/bleaching cycles. In other words, the light modulating composition solution has good stability.
[0015] A detailed description is given in the following embodiments with reference to the accompanying drawings.
Brief Description of the drawings
[0016] The disclosure can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
Fig. 1 shows a light modulating device in one embodiment of the disclosure;
Fig. 2 shows cyclic voltammetry diagrams of organic compounds in the Examples of the disclosure;
Fig. 3 shows cyclic voltammetry diagrams of organic compounds in the Examples of the disclosure;
Fig. 4 shows transmittance spectra of neutral and oxidation state of organic compounds in the Examples of the disclosure;
Fig. 5 shows transmittance spectra of neutral and oxidation state of organic compounds in the Examples of the disclosure;
Fig. 6 shows transmittance spectra of neutral and oxidation state of light modulating device in the Examples of the disclosure;
Fig. 7 shows transmittance spectra of a light modulating device after switching cycles in the Examples of the disclosure; and
Fig. 8 shows transmittance spectra after different voltages applied to a light modulating device in the Examples of the disclosure.
Detailed Description
[0017] In accordance with some embodiments of the disclosure, an organic compound is provided. The organic compound has a chemical structure represented by formula (I):
X-Ar-X (I)
wherein
[0018] In one embodiment, R1 can be a C1-8 alkyl group.
[0019] In one embodiment, R1 can be a C1-4 alkyl group.
[0020] In one embodiment, R2 can be hydrogen, a C1-8 alkyl group, or a C1-8 alkoxy group.
[0021] In one embodiment, R2 can be a C1-4 alkyl group, or a C1-4 alkoxy group.
[0022] In one embodiment, R3 can be hydrogen, a C1-8 alkyl group, or a C1-8 alkoxy group.
[0023] In one embodiment, R3 can be a C1-4 alkyl group, or a C1-4 alkoxy group.
[0024] The organic compounds can be prepared from the reaction of carboxylic acids with diamine. The intermediate product of the diamine, dinitro can be prepared according to literature methods and then the diamine can be obtained from the dinitro through reduction as shown in Formula 2 or 3 below (J. Polym. Sci. Part A: Polym. Chem. 2006, 44, pp4579-4592, the entire disclosure of which is incorporated herein by reference). Ar', Ar", and R2 in Formulas 2 and 3 have the same meaning as defined in the above Formula (1). The aforementioned organic compounds are applicable as an electrochromic element, a semiconductor, a solar cell, an organic electroluminescent element, an active substance of a non-linear material, etc.
[0025] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0026] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0027] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0028] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0029] According to an embodiment of the disclosure, the aforementioned organic compound can be used as a first oxidizable compound which can be combined with a reducible compound, an electrolyte and a solvent to form a light modulating composition. In one embodiment, the oxidizable compound and the electrolyte have a molar ratio of 1:1 to 1:20, and the reducible compound and the electrolyte have a molar ratio of 1:1 to 1:20.
[0030] In some embodiments, the electrolyte may contain at least one inert conducting salt. Examples of suitable inert conducting salts include lithium salts, sodium salts and tetraalkylammonium salts, such as tetrabutylammonium. Suitable solvents include solvents which are redox-inert at the voltages selected and which cannot dissociate to form electrophiles or nucleophiles or themselves react as sufficiently strong electrophiles or nucleophiles and thus could react with the colored ionic free radicals. Examples of suitable solvents include propylene carbonate (PC), gamma-Butyrolactone (GBL, γ-butyrolactone), acetonitrile, propionitrile, glutaronitrile, methylglutaronitrile, 3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane or mixtures thereof. The concentration of the electrolyte can be between 0.01M and 1.5M.
[0031] In some embodiments, the reducible compound can be selected from the group consisting of
[0032] In some embodiments of the disclosure, the oxidizable compound can include a second oxidizable compound, which can be
or the combinations thereof, wherein R8 is H or an alkyl group.
[0033] In accordance with some embodiments of the disclosure, a light modulating device can be provided. As shown in FIG. 1, the light modulating device includes a pair of electrodes, an isolating unit and a light modulating composition. The pair of electrodes 12, 18 includes a first transparent substrate 11 with a first transparent conductive layer 13 on a surface of the transparent substrate and a second transparent substrate 19 with a second transparent conductive layer 17 on a surface of the transparent substrate 19. The pair of electrodes 12, 18 is disposed by arranging the first transparent conductive layer 13 and second transparent conductive layer 17 to face each other. The isolating unit 14 is inserted and sealed up between the first and second transparent conductive layers 13, 17 to form a cell 15. Then, via a port (not shown) on the isolating unit 14, the aforementioned light modulating composition is introduced into the cell 15. The port was sealed so that the light modulating device 10 is formed.
[0034] In some embodiments of the disclosure, the transparent substrates can be made of glass or plastic such as polycarbonate. The conductive layer can be made of indium tin oxide (ITO), antimony- or fluorine-doped tin oxide, antimony- or aluminum-doped zinc oxide, tin oxide or conductive organic polymers such as, for example, optionally substituted polythienyls, polypyrroles, polyanilines, polyacetylene.
[0035] In some embodiments of the disclosure, the isolating unit can be formed by blending spacer elements with a thermosetting or photochemically curable adhesive. Spacer elements can be small spherules of plastic or glass or certain sand fractions.
[0036] In some embodiments of the disclosure, the distance from the first conducting material layer to the second conducting material layer can be between 10μm to 200μm.
[0037] The light modulating device will change from colorless to a specific color (e.g. yellow green, sky blue, blue, deep blue, or deep purple) after being applied with a suitable voltage. The specific color and the voltage depend on the chemical structure of the organic oxidizable compound of the light modulating composition. After the voltage is switched off, the cell contents completely bleach once more within 1 min. The experiments described below show that the cell still worked satisfactorily after operating 10,000 coloring/bleaching cycles. In other words, the light modulating composition solution has good stability.
[0038] Below, exemplary embodiments will be described in detail with reference to the accompanying drawings so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout.
Examples
[0039] In the following Examples, the electrochemical analysis was performed by CH Instruments 612C to scan potentials of the thin film. The cyclic voltammetry (CV) was performed by a three-electrode system, wherein the ITO glass served as a working electrode (the coated polymer had an area of about 2.0cm×0.8cm), an Ag/AgCl electrode (in saturated KCl solution) served as a reference electrode, a platinum wire served as an auxiliary electrode, 0.1M of tetrabutylammonium perchloride solution (in acetonitrile) served as an electrolyte, and a scan rate was 50mV/s. The average value of a redox potential was defined as a half-wave potential.
[0040] Example A1: Preparation of organic compound (A1)
[0041] 10.0 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 6.4 g of isobutyric acid (compound (II)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A1) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0042] The physical measurement of the compound (A1) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.02 (d, J = 7.0 Hz, 6H), 2.49 (m, 2H), 3.66 (s, 3H), 6.78 (d, J = 9.0 Hz, 4H), 6.81 (d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 9.0 Hz, 4H), 9.65 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 19.5, 34.8, 55.2, 114.8, 120.4, 122.9, 125.7, 133.9, 140.5, 143.0, 155.2, 174.8. Anal. calcd for C27H31N3O3：C, 72.78；H, 7.01；N, 9.43；found：C, 72.69；H, 7.03；N, 9.51.
[0043] The compound (A1) has a cyclic voltammetry CV diagram as shown in Fig. 2, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 4, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0044] Example A2: Preparation of organic compound (A2)
[0045] 10.0 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 8.4 g of cyclohexanoic acid (compound (III)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A2) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0046] The physical measurement of the compound (A2) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.13~1.44 (m, 10H), 1.63~1.79 (m, 10H), 2.29 (t, 2H), 3.72 (s, 3H), 6.84 (d, J = 9.0 Hz, 4H), 6.88 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 8.5 Hz, 2H), 7.48 (d, J = 9.0 Hz, 4H), 9.67 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 13.9, 22.0, 25.1, 28.5, 28.6, 31.2, 55.2, 114.8, 120.2, 122.8, 125.8, 140.5, 143.0, 155.24, 170.8. Anal. calcd for C33H39N3O3：C, 75.4；H, 7.48；N,7.99；found：C, 74.8；H, 7.45；N, 7.87.
[0047] The compound (A2) has redox potential as tabulated in Table 1 below, transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0048] Example A3: Preparation of organic compound (A3)
[0049] 10.0 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 9.45 g of octanoic acid (compound (IV)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A3) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0050] The physical measurement of the compound (A3) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 0.86 (t, 6H), 1.26~1.59 (m, 16H), 2.51 (t, 4H), 3.73 (s, 3H), 6.85 (d, J = 9.0 Hz, 4H), 6.88 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 9.0 Hz, 4H), 9.76 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 13.9, 22.0, 25.2, 28.5, 28.6, 31.2, 55.2, 114.8, 120.2, 122.8, 125.8, 133.8, 140.5, 143.0, 155.2, 170.8. Anal. calcd for C33H43N3O3：C, 74.82；H, 8.18；N,7.93；found：C, 74.89；H, 8.09；N, 7.88.
[0051] The compound (A3) has redox potential as tabulated in Table 1 below, the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0052] Example A4: Preparation of organic compound (A4)
[0053] 10.0 g of 4-methoxypentaphenylamine-based diamine (compound (V)) and 5.1 g of cyclohexanoic acid (compound (III)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A4) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0054] The physical measurement of the compound (A4) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.24~1.38 (m, 10H), 1.40~1.75 (m, 10H), 1.77 (t, 2H), 3.72(s, 6H), 6.79 (s, 4H), 6.87~6.88 (m, 6H), 6.97 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 9.0 Hz, 4H), 9.69 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 25.2, 25.4, 29.1, 44.7, 55.2, 114.8, 120.3, 123.0, 123.2, 125.9, 134.0, 140.4, 142.0, 142.9, 155.3, 173.8. Anal. calcd for C46H52N4O4：C, 76.21；H, 7.23；N,7.73；found：C, 75.95；H, 7.29；N, 7.75.
[0055] The compound (A4) has a cyclic voltammetry CV diagram as shown in Fig. 3, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 5, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
Example B1: Preparation of organic compound (B1)
[0056] 1.50 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 1.70 g of hexahydrophthalic anhydride (compound (VI)) were mixed in a reaction flask. 2.5 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and a little of Isoquinoline serving as a catalyst was then added into the reaction flask. The mixture in the reaction flask was heated to 210℃ for 5 hours, and then cooled down to room temperature. The cooled reaction mixture was diluted by methanol and poured into water to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (B1) (beige solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0057] The physical measurement of the compound (B1) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.38 (m, 4H), 1.73 (q, 4H), 3.08 (q, 2H), 3.75 (s, 3H), 6.97 (d, J = 9.5 Hz, 2H), 7.02 (d, J = 9.0 Hz, 4H), 7.11 (d, J = 9.5 Hz, 2H), 7.14 (d, J = 9.0 Hz, 4H). 13C NMR (125 MHz, DMSO-d6)：δ 21.4, 23.4, 55.3, 115.4, 122.0, 126.2, 127.9, 128.1, 139.1, 147.0, 156.7, 178.8. Anal. calcd for C35H35N3O5：C, 72.77；H, 6.11；N, 7.27；found：C, 72.35；H, 6.16；N, 7.25.
[0058] The compound (B1) has a cyclic voltammetry CV diagram as shown in Fig. 2, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 4, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
Example B2: Preparation of organic compound (B2)
[0059] 5.0 g of 4-methoxypentaphenylamine-based diamine (compound (V)) and 3.06 g of hexahydrophthalic anhydride (compound (VI)) were mixed in a reaction flask. 7.5 ml of dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and a little of isoquinoline serving as a catalyst was then added into the reaction flask. The mixture in the reaction flask was heated to 210℃ for 5 hours, and then cooled to room temperature. The cooled reaction mixture was diluted by methanol and poured into water to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (B2) (beige solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0060] The physical measurement of the compound (B2) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.36~1.42 (m, 8H), 1.70~2.00 (m, 8H), 3.08 (t, 4H), 3.74 (s, 6H), 6.92~7.10 (m, 20H). 13C NMR (125 MHz, DMSO-d6)：δ 21.3, 21.4, 23.3, 55.2, 115.2, 120.2, 124.9, 125.0, 127.5, 127.7, 139.4, 142.2, 147.6, 156.3, 178.8. Anal. calcd for C48H46N4O6：C, 74.40；H, 5.98；N, 7.23；found：C, 74.21；H, 6.03；N, 7.27.
[0061] The compound (B2) has a cyclic voltammetry CV diagram as shown in Fig. 3, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 5, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0062] Table 1, Table 2 and Fig. 1 show that triphenylamine system (compounds A1-A3 and B1) only had an oxidation-reducing peak and pentaphenyldiamine system (compounds A4 and B2) had two oxidation-reducing peaks. The difference of electrical potential peak between the amido group and the imido group was large (A1 vs. B1, and A4 vs. B2). By using different terminal functional groups, the redox potential of an organic compound can be modulated.
[0063] Table 2, Fig. 3 and Fig. 4 show that the shielding effect of the triphenylamine system (compounds A1 and B1) was better than the shielding effect of PSN in the visible region. The pentaphenyldiamine system had absorption in the visible region and good heat-ray absorption in the NIR region. In. other words, the pentaphenyldiamine system compounds had property of anti-ultraviolet activity and absorption in the NIR region.
[0064] Example C1: Preparation of a light modulating device
[0065] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A2 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A2 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.4V to measure the transmittance of the device as tabulated in Table 3 below.
[0066] Example C2: Preparation of a light modulating device
[0067] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound B1 and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound B1 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.6V to measure the transmittance of the device as tabulated in Table 3 below. The transmission spectrum of the neutral state (off-state) and oxidation state (on-state) of the device obtained as shown in FIG. 6.
[0068] Example C3: Preparation of a light modulating device
[0069] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A4 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A4 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.1V to measure the transmittance of the device as tabulated in Table 3 below.
[0070] Example C4: Preparation of a light modulating device
[0071] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound B2 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound B2 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.3V to measure the transmittance of the device as tabulated in Table 3 below.
[0072] Table 3 and Fig. 6 show that the shielding effect of the Examples with added viologen was increased at wavelength around 600 nm. The shielding effect of the pentaphenyldiamine system Example C3 and C4 were larger than the shielding effect of the compounds C1 and C2 at wavelength near 400-500 nm. Compared with PSN, all Examples had the shielding effect within the range of 350-800 nm because triphenylamine and pentaphenyldiamine systems had better conjugation properties.
[0073] Example D: Preparation of a light modulating device
[0074] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0075] The light modulating device was applied a voltage of 1.3V for 3.250 seconds (on-state), and was applied a voltage of -1.3V for 0.375 seconds (off-state), and then stay at 0V for 3.675 seconds. Repeating the above method, the device was subjected to a cycle life test. As shown in the transmission spectrum of Fig. 7, the device turned from the original neutral state which was completely free of absorption to deep blue (oxidation state) in the visible region. Moreover, After 10,000 on/off cycles the device still worked and had transmission spectrum of on/off so that the device is stable. The transmission of the device at different wavelengths and at different state was obtained and as tabulated in Table 4 below.
[0076] Example E: Preparation of a transparent-green complementary light modulating device
[0077] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1, 5,10-dimethylphenazine (DMP) and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.025M, the concentration of DMP was 0.025M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0078] When the light modulating device was applied a voltage gradually to 1.3V, the spectrum shows that transmission of the device reduced to 10.4% at a wavelength of 450 nm. The device turned from transparent at neutral state to deep green (oxidation state). Moreover, after switching off the voltage the device can be recovered to transparent (off-state) in 1 second.
[0079] Example F: Preparation of a transparent-deep blue complementary light modulating device
[0080] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1, phenothiazine (PSN), methylphenothiazine (MePSN) and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.05M, the concentration of PSN was 0.05M, the concentration of MePSN was 0.05M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0081] When the light modulating device was applied a voltage gradually to 1.3V, the spectrum shows that transmission of the device reduced to 10.4% at a wavelength of 450 nm. The device turned from transparent at neutral state to deep green (oxidation state). Moreover, After switching off the voltage the device can be recovered to transparent (off-state) in 1 second.
[0082] Example G: Preparation of a transparent-dark complementary light modulating device
[0083] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1, phenothiazine (PSN), methylphenothiazine (MePSN) and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.1M, the concentration of PSN was 0.1M, the concentration of MePSN was 0.1M and the concentration of viologen was 0.1M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0084] When the light modulating device was applied a voltage gradually to 1.3V, the spectrum shows that transmission of the device reduced to 10.4% at a wavelength of 450 nm. The device turned from transparent at neutral state to deep green (oxidation state). The transmission spectrum of the device at different wavelengths and at different state was obtained and as shown in FIG. 8. Moreover, After switching off the voltage the device can be recovered to transparent (off-state) in 1 second.
[0085] Comparative Example H: Preparation of a light modulating device
[0086] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, phenothiazine (PSN) and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of PSN was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The transmittance spectrum of neutral and oxidation state was shown in Fig. 4, and the transmittance of neutral and oxidation state at different wavelength was tabulated in Table 2.
[0087] When the light modulating device was applied a voltage gradually to 1.3V, the device turned from transparent at neutral state to deep blue (oxidation state). The transmission spectrum of the device at different wavelengths and at different state was obtained and as shown in FIG. 6. The transmittance of the device at different wavelength was tabulated in Table 3.
[0088] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims and their equivalents.
Cross reference to related Applications
[0001] This Application claims priority of Taiwan Patent Application No.104138432, filed on November 20, 2015, the entirety of which is incorporated by reference herein.
Technical Field
[0002] The present disclosure relates to organic compounds, light modulating compositions, and light modulating devices employing the same.
Background
[0003] Light modulating devices are attractive in green energy industries due to their low driving voltage and bistability. Recently, the major part of light modulating material is inorganic oxides for longer lifetime and endurance, however, films thereof are prepared by using expensive processes and equipment such as vacuum deposition, spray pyrolysis, or sputtering. Even ignoring the cost of processing, the inorganic oxide still has shortcomings such as a slow electrochromic rate, less color variation, and the like. In an organic system, light modulating organic materials use conjugated polymer with more color variation and fast electrochromic rates. However, the conjugated compound has shortcomings such as expensive monomers, complicated synthesis, and formation by electro-polymerization. The electrochromic conjugated polymer has an appearance of deep color due to its conjugated length. Although the deep color can be lightened by applying a voltage, the conjugated polymer cannot be fully transparent. In other words, the conjugated polymer must be electrified to effect a transparent state, thereby leading to the problem of high energy consumption.
[0004] Accordingly, there is a need for a novel electrochromic organic material to meet the requirements of transparency, film-firming ability, and electrochromicity.
[0005] Patent Document: U.S. Pub. No. 20090231663.
Disclosure of the invention
[0006] Problems to be solved
[0007] The conjugated compound has shortcomings such as expensive monomers, complicated synthesis, and formation by electro-polymerization. The electrochromic conjugated polymer has an appearance of deep color due to its conjugated length. Although the deep color can be lightened by applying a voltage, the conjugated polymer cannot be fully transparent. In other words, the conjugated polymer must be electrified to effect a transparent state, thereby leading to the problem of high energy consumption.
[0008] Means for solving the problems
[0009] The present disclosure relates to organic compounds, light modulating compositions, and light modulating devices employing the same.
[0010] In accordance with one embodiment of the disclosure, an organic compound is provided. The organic compound has a chemical structure represented by formula (I):
X-Ar-X (I)
wherein
[0011] In accordance with another embodiment of the disclosure, a light modulating composition is provided. The composition includes a first oxidizable compound, a reducible compound, an electrolyte and a solvent, wherein the first oxidizable compound includes the aforementioned organic compound.
[0012] In accordance with another embodiment of the disclosure, a light modulating device is provided. The light modulating device includes a pair of electrodes, an isolating unit and a light modulating composition. The pair of electrodes includes a first transparent substrate with a first transparent conductive layer on a surface of the transparent substrate and a second transparent substrate with a second transparent conductive layer on a surface of the transparent substrate. The pair of electrodes is disposed by arranging the first transparent conductive layer and the second transparent conductive layer to face each other. The isolating unit inserted between the first and second transparent conductive layers to form a cell. Then, the light modulating composition is filled in the cell. The composition includes a first oxidizable compound, a reducible compound, an electrolyte and a solvent. The first oxidizable compound includes the aforementioned organic compounds.
[0013] Effect of the invention
[0014] The light modulating device will change from colorless to a specific color (e.g. yellow green, sky blue, blue, deep blue, or deep purple) after being applied with a suitable voltage. The specific color and the voltage depend on the chemical structure of the organic oxidizable compound of the light modulating composition. After the voltage is switched off, the cell contents completely bleach once more within 1 min. The cell still work well after operating 10,000 coloring/bleaching cycles. In other words, the light modulating composition solution has good stability.
[0015] A detailed description is given in the following embodiments with reference to the accompanying drawings.
Brief Description of the drawings
[0016] The disclosure can be more fully understood by reading the subsequent detailed description and examples with references made to the accompanying drawings, wherein:
Fig. 1 shows a light modulating device in one embodiment of the disclosure;
Fig. 2 shows cyclic voltammetry diagrams of organic compounds in the Examples of the disclosure;
Fig. 3 shows cyclic voltammetry diagrams of organic compounds in the Examples of the disclosure;
Fig. 4 shows transmittance spectra of neutral and oxidation state of organic compounds in the Examples of the disclosure;
Fig. 5 shows transmittance spectra of neutral and oxidation state of organic compounds in the Examples of the disclosure;
Fig. 6 shows transmittance spectra of neutral and oxidation state of light modulating device in the Examples of the disclosure;
Fig. 7 shows transmittance spectra of a light modulating device after switching cycles in the Examples of the disclosure; and
Fig. 8 shows transmittance spectra after different voltages applied to a light modulating device in the Examples of the disclosure.
Detailed Description
[0017] In accordance with some embodiments of the disclosure, an organic compound is provided. The organic compound has a chemical structure represented by formula (I):
X-Ar-X (I)
wherein
[0018] In one embodiment, R1 can be a C1-8 alkyl group.
[0019] In one embodiment, R1 can be a C1-4 alkyl group.
[0020] In one embodiment, R2 can be hydrogen, a C1-8 alkyl group, or a C1-8 alkoxy group.
[0021] In one embodiment, R2 can be a C1-4 alkyl group, or a C1-4 alkoxy group.
[0022] In one embodiment, R3 can be hydrogen, a C1-8 alkyl group, or a C1-8 alkoxy group.
[0023] In one embodiment, R3 can be a C1-4 alkyl group, or a C1-4 alkoxy group.
[0024] The organic compounds can be prepared from the reaction of carboxylic acids with diamine. The intermediate product of the diamine, dinitro can be prepared according to literature methods and then the diamine can be obtained from the dinitro through reduction as shown in Formula 2 or 3 below (J. Polym. Sci. Part A: Polym. Chem. 2006, 44, pp4579-4592, the entire disclosure of which is incorporated herein by reference). Ar', Ar", and R2 in Formulas 2 and 3 have the same meaning as defined in the above Formula (1). The aforementioned organic compounds are applicable as an electrochromic element, a semiconductor, a solar cell, an organic electroluminescent element, an active substance of a non-linear material, etc.
[0025] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0026] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0027] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0028] In accordance with some embodiments of the disclosure, the disclosure also provides an organic compound having a structure represented by the following formula:
[0029] According to an embodiment of the disclosure, the aforementioned organic compound can be used as a first oxidizable compound which can be combined with a reducible compound, an electrolyte and a solvent to form a light modulating composition. In one embodiment, the oxidizable compound and the electrolyte have a molar ratio of 1:1 to 1:20, and the reducible compound and the electrolyte have a molar ratio of 1:1 to 1:20.
[0030] In some embodiments, the electrolyte may contain at least one inert conducting salt. Examples of suitable inert conducting salts include lithium salts, sodium salts and tetraalkylammonium salts, such as tetrabutylammonium. Suitable solvents include solvents which are redox-inert at the voltages selected and which cannot dissociate to form electrophiles or nucleophiles or themselves react as sufficiently strong electrophiles or nucleophiles and thus could react with the colored ionic free radicals. Examples of suitable solvents include propylene carbonate (PC), gamma-Butyrolactone (GBL, γ-butyrolactone), acetonitrile, propionitrile, glutaronitrile, methylglutaronitrile, 3,3'-oxydipropionitrile, hydroxypropionitrile, dimethylformamide, N-methylpyrrolidone, sulfolane, 3-methylsulfolane or mixtures thereof. The concentration of the electrolyte can be between 0.01M and 1.5M.
[0031] In some embodiments, the reducible compound can be selected from the group consisting of
[0032] In some embodiments of the disclosure, the oxidizable compound can include a second oxidizable compound, which can be
or the combinations thereof, wherein R8 is H or an alkyl group.
[0033] In accordance with some embodiments of the disclosure, a light modulating device can be provided. As shown in FIG. 1, the light modulating device includes a pair of electrodes, an isolating unit and a light modulating composition. The pair of electrodes 12, 18 includes a first transparent substrate 11 with a first transparent conductive layer 13 on a surface of the transparent substrate and a second transparent substrate 19 with a second transparent conductive layer 17 on a surface of the transparent substrate 19. The pair of electrodes 12, 18 is disposed by arranging the first transparent conductive layer 13 and second transparent conductive layer 17 to face each other. The isolating unit 14 is inserted and sealed up between the first and second transparent conductive layers 13, 17 to form a cell 15. Then, via a port (not shown) on the isolating unit 14, the aforementioned light modulating composition is introduced into the cell 15. The port was sealed so that the light modulating device 10 is formed.
[0034] In some embodiments of the disclosure, the transparent substrates can be made of glass or plastic such as polycarbonate. The conductive layer can be made of indium tin oxide (ITO), antimony- or fluorine-doped tin oxide, antimony- or aluminum-doped zinc oxide, tin oxide or conductive organic polymers such as, for example, optionally substituted polythienyls, polypyrroles, polyanilines, polyacetylene.
[0035] In some embodiments of the disclosure, the isolating unit can be formed by blending spacer elements with a thermosetting or photochemically curable adhesive. Spacer elements can be small spherules of plastic or glass or certain sand fractions.
[0036] In some embodiments of the disclosure, the distance from the first conducting material layer to the second conducting material layer can be between 10μm to 200μm.
[0037] The light modulating device will change from colorless to a specific color (e.g. yellow green, sky blue, blue, deep blue, or deep purple) after being applied with a suitable voltage. The specific color and the voltage depend on the chemical structure of the organic oxidizable compound of the light modulating composition. After the voltage is switched off, the cell contents completely bleach once more within 1 min. The experiments described below show that the cell still worked satisfactorily after operating 10,000 coloring/bleaching cycles. In other words, the light modulating composition solution has good stability.
[0038] Below, exemplary embodiments will be described in detail with reference to the accompanying drawings so as to be easily realized by a person having ordinary knowledge in the art. The inventive concept may be embodied in various forms without being limited to the exemplary embodiments set forth herein. Descriptions of well-known parts are omitted for clarity, and like reference numerals refer to like elements throughout.
Examples
[0039] In the following Examples, the electrochemical analysis was performed by CH Instruments 612C to scan potentials of the thin film. The cyclic voltammetry (CV) was performed by a three-electrode system, wherein the ITO glass served as a working electrode (the coated polymer had an area of about 2.0cm×0.8cm), an Ag/AgCl electrode (in saturated KCl solution) served as a reference electrode, a platinum wire served as an auxiliary electrode, 0.1M of tetrabutylammonium perchloride solution (in acetonitrile) served as an electrolyte, and a scan rate was 50mV/s. The average value of a redox potential was defined as a half-wave potential.
[0040] Example A1: Preparation of organic compound (A1)
[0041] 10.0 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 6.4 g of isobutyric acid (compound (II)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A1) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0042] The physical measurement of the compound (A1) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.02 (d, J = 7.0 Hz, 6H), 2.49 (m, 2H), 3.66 (s, 3H), 6.78 (d, J = 9.0 Hz, 4H), 6.81 (d, J = 8.5 Hz, 2H), 6.87 (d, J = 8.5 Hz, 2H), 7.41 (d, J = 9.0 Hz, 4H), 9.65 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 19.5, 34.8, 55.2, 114.8, 120.4, 122.9, 125.7, 133.9, 140.5, 143.0, 155.2, 174.8. Anal. calcd for C27H31N3O3：C, 72.78；H, 7.01；N, 9.43；found：C, 72.69；H, 7.03；N, 9.51.
[0043] The compound (A1) has a cyclic voltammetry CV diagram as shown in Fig. 2, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 4, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0044] Example A2: Preparation of organic compound (A2)
[0045] 10.0 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 8.4 g of cyclohexanoic acid (compound (III)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A2) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0046] The physical measurement of the compound (A2) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.13~1.44 (m, 10H), 1.63~1.79 (m, 10H), 2.29 (t, 2H), 3.72 (s, 3H), 6.84 (d, J = 9.0 Hz, 4H), 6.88 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 8.5 Hz, 2H), 7.48 (d, J = 9.0 Hz, 4H), 9.67 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 13.9, 22.0, 25.1, 28.5, 28.6, 31.2, 55.2, 114.8, 120.2, 122.8, 125.8, 140.5, 143.0, 155.24, 170.8. Anal. calcd for C33H39N3O3：C, 75.4；H, 7.48；N,7.99；found：C, 74.8；H, 7.45；N, 7.87.
[0047] The compound (A2) has redox potential as tabulated in Table 1 below, transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0048] Example A3: Preparation of organic compound (A3)
[0049] 10.0 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 9.45 g of octanoic acid (compound (IV)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A3) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0050] The physical measurement of the compound (A3) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 0.86 (t, 6H), 1.26~1.59 (m, 16H), 2.51 (t, 4H), 3.73 (s, 3H), 6.85 (d, J = 9.0 Hz, 4H), 6.88 (d, J = 8.5 Hz, 2H), 6.95 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 9.0 Hz, 4H), 9.76 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 13.9, 22.0, 25.2, 28.5, 28.6, 31.2, 55.2, 114.8, 120.2, 122.8, 125.8, 133.8, 140.5, 143.0, 155.2, 170.8. Anal. calcd for C33H43N3O3：C, 74.82；H, 8.18；N,7.93；found：C, 74.89；H, 8.09；N, 7.88.
[0051] The compound (A3) has redox potential as tabulated in Table 1 below, the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0052] Example A4: Preparation of organic compound (A4)
[0053] 10.0 g of 4-methoxypentaphenylamine-based diamine (compound (V)) and 5.1 g of cyclohexanoic acid (compound (III)) were mixed in a reaction flask. 25 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and 20.3 g of Triphenyl Phosphate (TPP) and 5.68 g of pyridine serving as a catalyst were then added into the reaction flask. The mixture in the reaction flask was heated to 105℃ for 4 hours, and then cooled down to room temperature. The cooled reaction mixture was poured into ethanol to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (A4) (white solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0054] The physical measurement of the compound (A4) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.24~1.38 (m, 10H), 1.40~1.75 (m, 10H), 1.77 (t, 2H), 3.72(s, 6H), 6.79 (s, 4H), 6.87~6.88 (m, 6H), 6.97 (d, J = 8.5 Hz, 2H), 7.47 (d, J = 9.0 Hz, 4H), 9.69 (s, 2H). 13C NMR (125 MHz, DMSO-d6)：δ 25.2, 25.4, 29.1, 44.7, 55.2, 114.8, 120.3, 123.0, 123.2, 125.9, 134.0, 140.4, 142.0, 142.9, 155.3, 173.8. Anal. calcd for C46H52N4O4：C, 76.21；H, 7.23；N,7.73；found：C, 75.95；H, 7.29；N, 7.75.
[0055] The compound (A4) has a cyclic voltammetry CV diagram as shown in Fig. 3, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 5, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
Example B1: Preparation of organic compound (B1)
[0056] 1.50 g of 4-methoxytriphenylamine-based diamine (compound (I)) and 1.70 g of hexahydrophthalic anhydride (compound (VI)) were mixed in a reaction flask. 2.5 ml of Dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and a little of Isoquinoline serving as a catalyst was then added into the reaction flask. The mixture in the reaction flask was heated to 210℃ for 5 hours, and then cooled down to room temperature. The cooled reaction mixture was diluted by methanol and poured into water to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (B1) (beige solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0057] The physical measurement of the compound (B1) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.38 (m, 4H), 1.73 (q, 4H), 3.08 (q, 2H), 3.75 (s, 3H), 6.97 (d, J = 9.5 Hz, 2H), 7.02 (d, J = 9.0 Hz, 4H), 7.11 (d, J = 9.5 Hz, 2H), 7.14 (d, J = 9.0 Hz, 4H). 13C NMR (125 MHz, DMSO-d6)：δ 21.4, 23.4, 55.3, 115.4, 122.0, 126.2, 127.9, 128.1, 139.1, 147.0, 156.7, 178.8. Anal. calcd for C35H35N3O5：C, 72.77；H, 6.11；N, 7.27；found：C, 72.35；H, 6.16；N, 7.25.
[0058] The compound (B1) has a cyclic voltammetry CV diagram as shown in Fig. 2, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 4, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
Example B2: Preparation of organic compound (B2)
[0059] 5.0 g of 4-methoxypentaphenylamine-based diamine (compound (V)) and 3.06 g of hexahydrophthalic anhydride (compound (VI)) were mixed in a reaction flask. 7.5 ml of dimethylacetamide (DMAc) serving as a solvent was added into the reaction flask, and a little of isoquinoline serving as a catalyst was then added into the reaction flask. The mixture in the reaction flask was heated to 210℃ for 5 hours, and then cooled to room temperature. The cooled reaction mixture was diluted by methanol and poured into water to precipitate a solid, and then filtered to collect the solid. The solid was washed by water and then dried, a compound (B2) (beige solid) was obtained. The synthesis pathway of the above reaction was as follows:
[0060] The physical measurement of the compound (B2) is listed below: 1H NMR (500 MHz, DMSO-d6)：δ 1.36~1.42 (m, 8H), 1.70~2.00 (m, 8H), 3.08 (t, 4H), 3.74 (s, 6H), 6.92~7.10 (m, 20H). 13C NMR (125 MHz, DMSO-d6)：δ 21.3, 21.4, 23.3, 55.2, 115.2, 120.2, 124.9, 125.0, 127.5, 127.7, 139.4, 142.2, 147.6, 156.3, 178.8. Anal. calcd for C48H46N4O6：C, 74.40；H, 5.98；N, 7.23；found：C, 74.21；H, 6.03；N, 7.27.
[0061] The compound (B2) has a cyclic voltammetry CV diagram as shown in Fig. 3, redox potential as tabulated in Table 1 below, the transmittance spectrum of neutral and oxidation state as shown in Fig. 5, and the transmittance of neutral and oxidation state at different wavelengths as tabulated in Table 2 below.
[0062] Table 1, Table 2 and Fig. 1 show that triphenylamine system (compounds A1-A3 and B1) only had an oxidation-reducing peak and pentaphenyldiamine system (compounds A4 and B2) had two oxidation-reducing peaks. The difference of electrical potential peak between the amido group and the imido group was large (A1 vs. B1, and A4 vs. B2). By using different terminal functional groups, the redox potential of an organic compound can be modulated.
[0063] Table 2, Fig. 3 and Fig. 4 show that the shielding effect of the triphenylamine system (compounds A1 and B1) was better than the shielding effect of PSN in the visible region. The pentaphenyldiamine system had absorption in the visible region and good heat-ray absorption in the NIR region. In. other words, the pentaphenyldiamine system compounds had property of anti-ultraviolet activity and absorption in the NIR region.
[0064] Example C1: Preparation of a light modulating device
[0065] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A2 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A2 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.4V to measure the transmittance of the device as tabulated in Table 3 below.
[0066] Example C2: Preparation of a light modulating device
[0067] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound B1 and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound B1 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.6V to measure the transmittance of the device as tabulated in Table 3 below. The transmission spectrum of the neutral state (off-state) and oxidation state (on-state) of the device obtained as shown in FIG. 6.
[0068] Example C3: Preparation of a light modulating device
[0069] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A4 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A4 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.1V to measure the transmittance of the device as tabulated in Table 3 below.
[0070] Example C4: Preparation of a light modulating device
[0071] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound B2 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound B2 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The light modulating device was applied a voltage of 1.3V to measure the transmittance of the device as tabulated in Table 3 below.
[0072] Table 3 and Fig. 6 show that the shielding effect of the Examples with added viologen was increased at wavelength around 600 nm. The shielding effect of the pentaphenyldiamine system Example C3 and C4 were larger than the shielding effect of the compounds C1 and C2 at wavelength near 400-500 nm. Compared with PSN, all Examples had the shielding effect within the range of 350-800 nm because triphenylamine and pentaphenyldiamine systems had better conjugation properties.
[0073] Example D: Preparation of a light modulating device
[0074] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1 and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0075] The light modulating device was applied a voltage of 1.3V for 3.250 seconds (on-state), and was applied a voltage of -1.3V for 0.375 seconds (off-state), and then stay at 0V for 3.675 seconds. Repeating the above method, the device was subjected to a cycle life test. As shown in the transmission spectrum of Fig. 7, the device turned from the original neutral state which was completely free of absorption to deep blue (oxidation state) in the visible region. Moreover, After 10,000 on/off cycles the device still worked and had transmission spectrum of on/off so that the device is stable. The transmission of the device at different wavelengths and at different state was obtained and as tabulated in Table 4 below.
[0076] Example E: Preparation of a transparent-green complementary light modulating device
[0077] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1, 5,10-dimethylphenazine (DMP) and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.025M, the concentration of DMP was 0.025M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0078] When the light modulating device was applied a voltage gradually to 1.3V, the spectrum shows that transmission of the device reduced to 10.4% at a wavelength of 450 nm. The device turned from transparent at neutral state to deep green (oxidation state). Moreover, after switching off the voltage the device can be recovered to transparent (off-state) in 1 second.
[0079] Example F: Preparation of a transparent-deep blue complementary light modulating device
[0080] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1, phenothiazine (PSN), methylphenothiazine (MePSN) and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.05M, the concentration of PSN was 0.05M, the concentration of MePSN was 0.05M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0081] When the light modulating device was applied a voltage gradually to 1.3V, the spectrum shows that transmission of the device reduced to 10.4% at a wavelength of 450 nm. The device turned from transparent at neutral state to deep green (oxidation state). Moreover, After switching off the voltage the device can be recovered to transparent (off-state) in 1 second.
[0082] Example G: Preparation of a transparent-dark complementary light modulating device
[0083] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, compound A1, phenothiazine (PSN), methylphenothiazine (MePSN) and viologen [(HV(BF4)2] were dissolved in the above solution to form a light modulating composition solution, wherein the concentration of compound A1 was 0.1M, the concentration of PSN was 0.1M, the concentration of MePSN was 0.1M and the concentration of viologen was 0.1M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm.
[0084] When the light modulating device was applied a voltage gradually to 1.3V, the spectrum shows that transmission of the device reduced to 10.4% at a wavelength of 450 nm. The device turned from transparent at neutral state to deep green (oxidation state). The transmission spectrum of the device at different wavelengths and at different state was obtained and as shown in FIG. 8. Moreover, After switching off the voltage the device can be recovered to transparent (off-state) in 1 second.
[0085] Comparative Example H: Preparation of a light modulating device
[0086] Tetrabutyl ammonium tetrafluoroborate (TBABF4) was dissolved in propylene carbonate (PC) to form a 0.5 M solution. Next, phenothiazine (PSN) and viologen [(HV(BF4)2] was dissolved in the above solution to form a light modulating composition solution, wherein the concentration of PSN was 0.1M and the concentration of viologen was 0.05M. Two ITO conductive glass plates were cut to the desired size and the ITO layers of the plates face each other. An isolating unit was connected with the two ITO conductive glass plates to construct a cell. Via a port on the isolating unit, the aforementioned light modulating composition is introduced into the cell so that the cell was filled with the light modulating composition solution. The port was sealed so that the light modulating device is formed. The distance between the glass plates was about 50μm. The transmittance spectrum of neutral and oxidation state was shown in Fig. 4, and the transmittance of neutral and oxidation state at different wavelength was tabulated in Table 2.
[0087] When the light modulating device was applied a voltage gradually to 1.3V, the device turned from transparent at neutral state to deep blue (oxidation state). The transmission spectrum of the device at different wavelengths and at different state was obtained and as shown in FIG. 6. The transmittance of the device at different wavelength was tabulated in Table 3.
[0088] It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary only, with the true scope of the disclosure being indicated by the following claims and their equivalents.
1. An organic compound, having a structure as defined by Formula (I):
X-Ar-X (I)
wherein
2. The organic compound as claimed in claim 1, wherein R1 is a C1-8 alkyl group; R2 is hydrogen, a C1-8 alkyl group, or a C1-8 alkoxy group; R3 is hydrogen, a C1-8 alkyl group, or a C1-8 alkoxy group.
3. The organic compound as claimed in claim 1, wherein the compound is represented by the following formula:
4. A light modulating composition, comprising:
a first oxidizable compound, wherein the first oxidizable compound is as claimed in claim 1;
a reducible compound;
an electrolyte; and
a solvent.
5. The light modulating composition as claimed in claim 9, wherein the electrolyte is an organic ammonium salt or an inorganic lithium salt.
6. The light modulating composition as claimed in claim 9, wherein the oxidizable compound and the electrolyte have a mole ratio of 1:1 to 1:20, the reducible compound and the electrolyte have a mole ratio of 1:1 to 1:20, and the concentration of the electrolyte is between 0.01M and 1.5M.
7. The light modulating composition as claimed in claim 9, wherein the reducible compound is selected from the group consisting of
8. The light modulating composition as claimed in claim 9, further comprising a second oxidizable compound selected from the group consisting of
9. A light modulating device, comprising:
a pair of electrodes, comprising:
a first transparent substrate with a first transparent conductive layer on a surface of the transparent substrate; and
a second transparent substrate with a second transparent conductive layer on a surface of the transparent substrate, disposed by arranging the first transparent conductive layer and the second transparent conductive layer to face each other;
an isolating unit, inserted between the first and second transparent conductive layers to form a cell; and
a light modulating composition filled in the cell,
wherein the light modulating composition comprises:
a first oxidizable compound, wherein the first oxidizable compound is as claimed in claim 1;
a reducible compound;
an electrolyte; and
a solvent.
1. Abstract
An organic compound, a light modulating composition and a light modulating device are provided. The organic compound has a chemical structure represented by formula (I):
X-Ar-X (I)
wherein
The organic compound is transparent in its neutral state. The amide group or imide group introduced into the aromatic amine not only enhances the solubility of the organic compound in the solvent, but also enhances the electrochemical stability of the organic compound.
2. Representative Drawing
Fig. 1
An organic compound, a light modulating composition and a light modulating device are provided. The organic compound has a chemical structure represented by formula (I):
X-Ar-X (I)
wherein
The organic compound is transparent in its neutral state. The amide group or imide group introduced into the aromatic amine not only enhances the solubility of the organic compound in the solvent, but also enhances the electrochemical stability of the organic compound.
2. Representative Drawing
Fig. 1
Fig. 1
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Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 2
Fig. 3
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Fig. 5
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Fig. 8