JP2004279795A - Non-resonant two-photon absorbing material and non-resonant two-photon emitting material, as well as non-resonant two-photon absorption inducing method and non-resonant two-photon emission generating method using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic material efficiently absorbing two photons, that is, an organic material having a large two-photon absorption sectional surface area. <P>SOLUTION: This non-resonant two-photon absorbing material contains an merocyanine coloring material performing non-resonant two-photon absorption. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００１３】
一般式（１）中、Ｚａ_３は５員または６員の含窒素複素環を形成する原子群を表わし、Ｚａ_４は５員または６員環を形成する原子群を表わす。
Ｒａ_３はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基を表す。
Ｍａ_８〜Ｍａ_１１はそれぞれ独立にメチン基を表わし、置換基を有していても良く、他のメチン基と環を形成しても良い。ｎａ^３は０または１であり、ｋａ^２は０〜８の整数を表わす。ｋａ^１が２以上の時、複数のＭａ_１０、Ｍａ_１１は同じでも異なってもよい。
ＣＩは電荷を中和するイオンを表わし、ｙは電荷の中和に必要な数を表わす。
（３）（２）にてｎａ^３が０であることを特徴とする（２）記載の非共鳴２光子吸収材料。
（４）該メロシアニン色素が下記一般式（２）にて表されることを特徴とする（１）〜（３）のいずれかに記載の非共鳴２光子吸収材料。
【００１４】
【化４】

【００１５】
一般式（２）中、Ｍａ_１０、Ｍａ_１１、Ｒａ_３、Ｚａ_４、ｋａ^２、ＣＩ、ｙは一般式（１）と同義である。Ｘ_１は−Ｏ−、−Ｓ−、−ＮＲ_３−、―ＣＲ_４Ｒ_５−のいずれかを表し、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基を表す。
Ｒ_１は置換基を表し、ａ１は０〜４の整数を表す。ａ１が２以上のとき、複数のＲ_１は同じでも異なっても良く、互いに連結して環を形成してもよい。
（５）（２）〜（４）にて、ｋａ^２が０〜４で表されることを特徴とする（２）〜（４）のいずれかに記載の非共鳴２光子吸収材料。
（６）（５）にて、ｋａ^２が２〜４で表されることを特徴とする（５）記載の非共鳴２光子吸収材料。
（７）（２）〜（６）にて、Ｒａ_３がアルキル基であることを特徴とする（２）〜（６）のいずれかに記載の非共鳴２光子吸収材料。
（８）（４）〜（７）にてＲ_３、Ｒ_４、Ｒ_５が共にアルキル基であることを特徴とする（４）〜（７）のいずれかに非共鳴２光子吸収材料。
（９）（４）〜（８）にて、Ｘ_１が−Ｏ−または―ＣＲ_４Ｒ_５−であることを特徴とする（４）〜（８）のいずれかに記載の非共鳴２光子吸収材料。
（１０）（２）〜（９）にて、Ｚａ_４から形成される環が、２−ピラゾロン−５−オン、ピラゾリジン−３，５−ジオン、ローダニン、インダン−１，３−ジオン、チオフェン−３−オン、チオフェン−３−オン−１，１−ジオキシド、１，３−ジオキサン−４，６−ジオン、バルビツール酸、２−チオバルビツール酸、クマリンー２，４−ジオンで表されることを特徴とする（２）〜（９）のいずれかに記載の非共鳴２光子吸収材料。
（１１）（１０）にて、Ｚａ_４から形成される環が、ピラゾリジン−３，５−ジオン、インダン−１，３−ジオン、１，３−ジオキサン−４，６−ジオン、バルビツール酸、２−チオバルビツール酸で表されることを特徴とする（１０）記載の非共鳴２光子吸収材料。
（１２）（１０）にて、Ｚａ_４から形成される環が、ピラゾリジン−３，５−ジオン、バルビツール酸、２−チオバルビツール酸で表されることを特徴とする（１０）記載の非共鳴２光子吸収材料。
（１３）（２）〜（１２）にて、Ｍａ_１０、Ｍａ_１１は無置換メチン基、メチル置換メチン基、エチル置換メチン基のいずれかで表されることを特徴とする（２）〜（１２）のいずれかに記載の非共鳴２光子吸収材料。
（１４）（１）〜（１３）に記載の非共鳴２光子吸収色素が２光子発光することを特徴とする非共鳴２光子発光色素とこれを含む非共鳴２光子発光材料。
（１５）（１）〜（１３）に記載の非共鳴２光子吸収色素に、該色素の有する線形吸収帯よりも長波長のレーザー光を照射して２光子吸収を誘起することを特徴とする非共鳴２光子吸収誘起方法。
（１６）（１）〜（１３）に記載の非共鳴２光子吸収色素に、該色素の有する線形吸収帯よりも長波長のレーザー光を照射して非共鳴２光子吸収を誘起し、発光を発生させることを特徴とする非共鳴２光子発光発生方法。
【００１６】
【発明の実施の形態】
以下に、本発明の非共鳴２光子吸収を行う化合物について詳しく説明する。
なお、本発明において、特定の部分を「基」と称した場合には、特に断りの無い限りは、一種以上の（可能な最多数までの）置換基で置換されていても、置換されていなくても良いことを意味する。例えば、「アルキル基」とは置換または無置換のアルキル基を意味する。また、本発明における化合物に使用できる置換基は、置換の有無にかかわらず、どのような置換基でも良い。
また、本発明において、特定の部分を「環」と称した場合、あるいは「基」に「環」が含まれる場合は、特に断りの無い限りは単環でも縮環でも良く、置換されていても置換されていなくても良い。
例えば、「アリール基」はフェニル基でもナフチル基でも良く、置換フェニル基でも良い。
【００１７】
ここで本発明の非共鳴２光子吸収を行うことを特徴とするメロシアニン色素について説明する。
なお、本発明にて色素とは、可視光領域（４００〜７００ｎｍ）及び／または近赤外領域（７００〜２０００ｎｍ）に吸収の一部を有する化合物に対する総称である。
【００１８】
メロシアニン色素とは、共役メチン鎖の両末端が酸素原子と窒素原子である色素の総称である。メロシアニン色素の具体例としては、Ｆ．Ｍ．Ｈａｒｍｅｒ著、Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃｏｍｐｏｕｎｄｓ−Ｃｙａｎｉｎｅ Ｄｙｅｓ ａｎｄ Ｒｅｌａｔｅｄ Ｃｏｍｐｏｕｎｄｓ、Ｊｏｈｎ＆Ｗｉｌｅｙ＆Ｓｏｎｓ 、Ｎｅｗ Ｙｏｒｋ、Ｌｏｎｄｏｎ、１９６４年刊に記載のものが挙げられる。
【００１９】
本発明の非共鳴２光子吸収を行うことを特徴とするメロシアニン色素はより好ましくは一般式（１）にて表されるメロシアニン色素である。
【００２０】
一般式（１）中、Ｚａ_３は５員または６員の含窒素複素環を形成する原子群を表わす。形成される５員または６員の含窒素複素環として好ましくは炭素原子数（以下Ｃ数という）３〜２５のオキサゾール核（例えば、２−３−メチルオキサゾリル、２−３−エチルオキサゾリル、２−３，４−ジエチルオキサゾリル、２−３−メチルベンゾオキサゾリル、２−３−エチルベンゾオキサゾリル、２−３−スルホエチルベンゾオキサゾリル、２−３−スルホプロピルベンゾオキサゾリル、２−３−メチルチオエチルベンゾオキサゾリル、２−３−メトキシエチルベンゾオキサゾリル、２−３−スルホブチルベンゾオキサゾリル、２−３−メチル−β−ナフトオキサゾリル、２−３−メチル−α−ナフトオキサゾリル、２−３−スルホプロピル−β−ナフトオキサゾリル、２−３−スルホプロピル−β−ナフトオキサゾリル、２−３−（３−ナフトキシエチル）ベンゾオキサゾリル、２−３，５−ジメチルベンゾオキサゾリル、２−６−クロロ−３−メチルベンゾオキサゾリル、２−５−ブロモ−３−メチルベンゾオキサゾリル、２−３−エチル−５−メトキシベンゾオキサゾリル、２−５−フェニル−３−スルホプロピルベンゾオキサゾリル、２−５−（４−ブロモフェニル）−３−スルホブチルベンゾオキサゾリル、２−３−ジメチル−５，６−ジメチルチオベンゾオキサゾリル）、Ｃ数３〜２５のチアゾール核（例えば、２−３−メチルチアゾリル、２−３−エチルチアゾリル、２−３−スルホプロピルチアゾリル、２−３−スルホブチルチアゾリル、２−３，４−ジメチルチアゾリル、２−３，４，４−トリメチルチアゾリル、２−３−カルボキシエチルチアゾリル、２−３−メチルベンゾチアゾリル、２−３−エチルベンゾチアゾリル、２−３−ブチルベンゾチアゾリル、２−３−スルホプロピルベンゾチアゾリル、２−３−スルホブチルベンゾチアゾリル、２−３−メチル−β−ナフトチアゾリル、２−３−スルホプロピル−γ−ナフトチアゾリル、２−３−（１−ナフトキシエチル）ベンゾチアゾリル、２−３，５−ジメチルベンゾチアゾリル、２−６−クロロ−３−メチルベンゾチアゾリル、２−６−ヨード−３−エチルベンゾチアゾリル、２−５−ブロモ−３−メチルベンゾチアゾリル、２−３−エチル−５−メトキシベンゾチアゾリル、２−５−フェニル−３−スルホプロピルベンゾチアゾリル、２−５−（４−ブロモフェニル）−３−スルホブチルベンゾチアゾリル、２−３−ジメチル−５，６−ジメチルチオベンゾチアゾリルなどが挙げられる）、Ｃ数３〜２５のイミダゾール核（例えば、２−１，３−ジエチルイミダゾリル、２−１，３−ジメチルイミダゾリル、２−１−メチルベンゾイミダゾリル、２−１，３，４−トリエチルイミダゾリル、２−１，３−ジエチルベンゾイミダゾリル、２−１，３，５−トリメチルベンゾイミダゾリル、２−６−クロロ−１，３−ジメチルベンゾイミダゾリル、２−５，６−ジクロロ−１，３−ジエチルベンゾイミダゾリル、２−１，３−ジスルホプロピル−５−シアノ−６−クロロベンゾイミダゾリルなどが挙げられる）、Ｃ数１０〜３０のインドレニン核（例えば、３，３−ジメチルインドレニン）、Ｃ数９〜２５のキノリン核（例えば、２−１−メチルキノリル、２−１−エチルキノリル、２−１−メチル６−クロロキノリル、２−１，３−ジエチルキノリル、２−１−メチル−６−メチルチオキノリル、２−１−スルホプロピルキノリル、４−１−メチルキノリル、４−１−スルホエチルキノリル、４−１−メチル−７−クロロキノリル、４−１，８−ジエチルキノリル、４−１−メチル−６−メチルチオキノリル、４−１−スルホプロピルキノリルなどが挙げられる）、Ｃ数３〜２５のセレナゾール核（例えば、２−３−メチルベンゾセレナゾリルなどが挙げられる）、Ｃ数５〜２５のピリジン核（例えば、２−ピリジルなどが挙げられる）などが挙げられ、さらに他にチアゾリン核、オキサゾリン核、セレナゾリン核、テルラゾリン核、テルラゾール核、ベンゾテルラゾール核、イミダゾリン核、イミダゾ［４，５−キノキザリン］核、オキサジアゾール核、チアジアゾール核、テトラゾール核、ピリミジン核を挙げることができる。
【００２１】
これら複素環は置換されても良く、置換基として好ましくは例えば、アルキル基（好ましくはＣ数１〜２０、例えば、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｎ−ペンチル、ベンジル、３−スルホプロピル、４−スルホブチル、カルボキシメチル、５−カルボキシペンチル）、アルケニル基（好ましくはＣ数２〜２０、例えば、ビニル、アリル、２−ブテニル、１，３−ブタジエニル）、シクロアルキル基（好ましくはＣ数３〜２０、例えばシクロペンチル、シクロヘキシル）、アリール基（好ましくはＣ数６〜２０、例えば、フェニル、２−クロロフェニル、４−メトキシフェニル、３−メチルフェニル、１−ナフチル）、ヘテロ環基（好ましくはＣ数１〜２０、例えば、ピリジル、チエニル、フリル、チアゾリル、イミダゾリル、ピラゾリル、ピロリジノ、ピペリジノ、モルホリノ）、アルキニル基（好ましくはＣ数２〜２０、例えば、エチニル、２−プロピニル、１，３−ブタジイニル、２−フェニルエチニル）、ハロゲン原子（例えば、Ｆ、Ｃｌ、Ｂｒ、Ｉ）、アミノ基（好ましくはＣ数０〜２０、例えば、アミノ、ジメチルアミノ、ジエチルアミノ、ジブチルアミノ、アニリノ）、シアノ基、ニトロ基、ヒドロキシル基、メルカプト基、カルボキシル基、スルホ基、ホスホン酸基、アシル基（好ましくはＣ数１〜２０、例えば、アセチル、ベンゾイル、サリチロイル、ピバロイル）、アルコキシ基（好ましくはＣ数１〜２０、例えば、メトキシ、ブトキシ、シクロヘキシルオキシ）、アリールオキシ基（好ましくはＣ数６〜２６、例えば、フェノキシ、１−ナフトキシ）、アルキルチオ基（好ましくはＣ数１〜２０、例えば、メチルチオ、エチルチオ）、アリールチオ基（好ましくはＣ数６〜２０、例えば、フェニルチオ、４−クロロフェニルチオ）、アルキルスルホニル基（好ましくはＣ数１〜２０、例えば、メタンスルホニル、ブタンスルホニル）、アリールスルホニル基（好ましくはＣ数６〜２０、例えば、ベンゼンスルホニル、パラトルエンンスルホニル）、スルファモイル基（好ましくはＣ数０〜２０、例えばスルファモイル、Ｎ−メチルスルファモイル、Ｎ−フェニルスルファモイル）、カルバモイル基（好ましくはＣ数１〜２０、例えば、カルバモイル、Ｎ−メチルカルバモイル、Ｎ、Ｎ−ジメチルカルバモイル、Ｎ−フェニルカルバモイル）、アシルアミノ基（好ましくはＣ数１〜２０、例えばアセチルアミノ、ベンゾイルアミノ）、イミノ基（好ましくはＣ数２〜２０、例えばフタルイミノ）、アシルオキシ基（好ましくはＣ数１〜２０、例えばアセチルオキシ、ベンゾイルオキシ）、アルコキシカルボニル基（好ましくはＣ数２〜２０、例えば、メトキシカルボニル、フェノキシカルボニル）、カルバモイルアミノ基（好ましくはＣ数１〜２０、例えばカルバモイルアミノ、Ｎ−メチルカルバモイルアミノ、Ｎ−フェニルカルバモイルアミノ）、であり、より好ましくは、アルキル基、アリール基、ヘテロ環基、ハロゲン原子、シアノ基、カルボキシル基、スルホ基、アルコキシ基、スルファモイル基、カルバモイル基、アルコキシカルボニル基である。
【００２２】
これらの複素環はさらに縮環されていてもよい。縮環する環として好ましくはベンゼン環、ベンゾフラン環、ピリジン環、ピロール環、インドール環、チオフェン環等が挙げられる。
【００２３】
Ｚａ_３により形成される５員または６員の含窒素複素環としてより好ましくは、オキサゾール核、イミダゾール核、チアゾール核、またはインドレニン環であり、さらに好ましくはオキサゾール核、またはインドレニン環である。
【００２４】
Ｚａ_４は５員または６員環を形成する原子群を表わす。Ｚａ_４から形成される環は一般に酸性核と呼ばれる部分であり、Ｊａｍｅｓ 編、Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ、第４版、マクミラン社、１９７７年、第１９８頁により定義される。 Ｚａ_４として好ましくは、２−ピラゾロン−５−オン、ピラゾリジン−３，５−ジオン、イミダゾリン−５−オン、ヒダントイン、２または４−チオヒダントイン、２−イミノオキサゾリジン−４−オン、２−オキサゾリン−５−オン、２−チオオキサゾリン−２，４−ジオン、イソローダニン、ローダニン、インダン−１，３−ジオン、チオフェン−３−オン、チオフェン−３−オン−１，１−ジオキシド、インドリン−２−オン、インドリン−３−オン、２−オキソインダゾリウム、５，７−ジオキソ−６，７−ジヒドロチアゾロ〔３，２−ａ 〕ピリミジン、３，４−ジヒドロイソキノリン−４−オン、１，３−ジオキサン−４，６−ジオン、バルビツール酸、２−チオバルビツール酸、クマリンー２，４−ジオン、インダゾリン−２−オン、ピリド［１，２−ａ］ピリミジン−１，３−ジオン、ピラゾロ〔１，５−ｂ〕キナゾロン、ピラゾロピリドンなどの核が挙げられる。
Ｚａ_４から形成される環としてより好ましくは、２−ピラゾロン−５−オン、ピラゾリジン−３，５−ジオン、ローダニン、インダン−１，３−ジオン、チオフェン−３−オン、チオフェン−３−オン−１，１−ジオキシド、１，３−ジオキサン−４，６−ジオン、バルビツール酸、２−チオバルビツール酸、クマリンー２，４−ジオンであり、さらに好ましくは、ピラゾリジン−３，５−ジオン、インダン−１，３−ジオン、１，３−ジオキサン−４，６−ジオン、バルビツール酸、２−チオバルビツール酸であり、最も好ましくはピラゾリジン−３，５−ジオン、バルビツール酸、２−チオバルビツール酸である。
【００２５】
Ｚａ_４から形成される環は置換されても良く、（好ましい置換基の例はＺａ_３上の置換基の例と同じ）置換基としてより好ましくは、アルキル基、アリール基、ヘテロ環基、ハロゲン原子、シアノ基、カルボキシル基、スルホ基、アルコキシ基、スルファモイル基、カルバモイル基、またはアルコキシカルボニル基である。
【００２６】
これらの複素環はさらに縮環されていてもよい。縮環する環として好ましくはベンゼン環、ベンゾフラン環、ピリジン環、ピロール環、インドール環、チオフェン環等が挙げられる。
【００２７】
Ｒａ_３はそれぞれ独立に、水素原子、アルキル基（好ましくはＣ数１〜２０、例えば、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｎ−ペンチル、ベンジル、３−スルホプロピル、４−スルホブチル、３−メチル−３−スルホプロピル、２’−スルホベンジル、カルボキシメチル、５−カルボキシペンチル）、アルケニル基（好ましくはＣ数２〜２０、例えば、ビニル、アリル）、アリール基（好ましくはＣ数６〜２０、例えば、フェニル、２−クロロフェニル、４−メトキシフェニル、３−メチルフェニル、１−ナフチル）、ヘテロ環基（好ましくはＣ数１〜２０、例えば、ピリジル、チエニル、フリル、チアゾリル、イミダゾリル、ピラゾリル、ピロリジノ、ピペリジノ、モルホリノ）であり、より好ましくはアルキル基（好ましくはＣ数１〜６のアルキル基）またはスルホアルキル基（好ましくは３−スルホプロピル、４−スルホブチル、３−メチル−３−スルホプロピル、２’−スルホベンジル）である。
【００２８】
Ｍａ_８〜Ｍａ_１１はそれぞれメチン基を表わし、置換基を有していても良く（好ましい置換基の例はＺａ_３及びＺａ_４上の置換基の例と同じ）、置換基として好ましくはアルキル基、ハロゲン原子、ニトロ基、アルコキシ基、アリール基、ニトロ基、ヘテロ環基、アリールオキシ基、アシルアミノ基、カルバモイル基、スルホ基、ヒドロキシ基、カルボキシ基、アルキルチオ基、シアノ基などが挙げられ、置換基としてより好ましくはアルキル基である。
Ｍａ_８〜Ｍａ_１１は無置換メチン基またはアルキル基（好ましくはＣ数１〜６）置換メチン基であることが好ましく、より好ましくは無置換、エチル基置換、メチル基置換のメチン基である。
Ｍａ_８〜Ｍａ_１１は互いに連結して環を形成しても良く、形成する環として好ましくはシクロヘキセン環、シクロペンテン環、ベンゼン環、チオフェン環等が挙げられる。
【００２９】
ｎａ^３は０または１であり、好ましくは０である。
【００３０】
ｋａ^２は０〜８の整数を表し、好ましくは０〜４の整数を表し、より好ましくは２〜４、さらに好ましくは２または３の整数を表す。
ｋａ^２が２以上の時、複数のＭａ_１０、Ｍａ_１１は同じでも異なってもよい。
【００３１】
ＣＩは電荷を中和するイオンを表わし、ｙは電荷の中和に必要な数を表わす。
【００３２】
本発明の非共鳴２光子吸収を行うことを特徴とするメロシアニン色素は一般式（２）にて表されることがより好ましい。
【００３３】
一般式（２）中、Ｍａ_１０、Ｍａ_１１、Ｒａ_３、Ｚａ_４、ｋａ^２、ＣＩ、ｙは一般式（１）と同義であり、好ましいものも同様である。
【００３４】
一般式（２）中、Ｘ_１は−Ｏ−、−Ｓ−、−ＮＲ_３−、―ＣＲ_４Ｒ_５−のいずれかを表し、Ｒ_３、Ｒ_４、Ｒ_５はそれぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基（以上好ましい例はＲａ_３と同じ）を表し、より好ましくはアルキル基を表す。
Ｘ_１は−Ｏ−または―ＣＲ_４Ｒ_５−であることが好ましい。
【００３５】
Ｒ_１は置換基を表し（好ましい置換基の例はＺａ_３上の置換基の例と同じ）、より好ましくは、アルキル基、アリール基、ヘテロ環基、ハロゲン原子、シアノ基、カルボキシル基、スルホ基、アルコキシ基、スルファモイル基、カルバモイル基、またはアルコキシカルボニル基である。
【００３６】
ａ１は０〜４の整数を表し、好ましくは０〜２を表し、より好ましくは０または１を表す。
ａ１が２以上のとき、複数のＲ_１は同じでも異なっても良く、互いに連結して環を形成してもよく、形成する環として好ましくはベンゼン環、ベンゾフラン環、ピリジン環、ピロール環、インドール環、チオフェン環等が挙げられる。
【００３７】
本発明のメロシアニン色素はモノマー状態で用いても良いが、会合状態で用いても良い。
ここで、色素発色団同士が特定の空間配置に、共有結合又は配位結合、あるいは種々の分子間力（水素結合、ファン・デル・ワールス力、クーロン力等）などの結合力によって固定されている状態を、一般的に会合（又は凝集）状態と称している。
【００３８】
参考のため、以下に会合体の説明を行う。会合体については、例えばジェイムス（Ｊａｍｅｓ）編「ザ・セオリー・オブ・ザ・フォトグラフィック・プロセス」（Ｔｈｅ Ｔｈｅｏｒｙ ｏｆ ｔｈｅ Ｐｈｏｔｏｇｒａｐｈｉｃ Ｐｒｏｃｅｓｓ）第４版、マクミラン出版社、１９７７年、第８章、第２１８〜２２２頁、及び小林孝嘉著「Ｊ会合体（Ｊ−Ａｇｇｒｅｇａｔｅｓ）」ワールド・サイエンティフィック・パブリッシング社（Ｗｏｒｌｄ Ｓｃｉｅｎｔｉｆｉｃ Ｐｕｂｌｉｓｈｉｎｇ Ｃｏ． Ｐｔｅ． Ｌｔｄ．）、１９９６年刊）などに詳細な説明がなされている。
モノマーとは単量体を意味する。会合体の吸収波長の観点では、モノマー吸収に対して、吸収が短波長にシフトする会合体をＨ会合体（２量体は特別にダイマーと呼ぶ）、長波長にシフトする会合体をＪ会合体と呼ぶ。
【００３９】
会合体の構造の観点では、レンガ積み会合体において、会合体のずれ角が小さい場合はＪ会合体と呼ばれるが、ずれ角が大きい場合はＨ会合体と呼ばれる。レンガ積み会合体については、ケミカル・フィジックス・レター（ＣｈｅｍｉｃａｌＰｈｙｓｉｃｓ Ｌｅｔｔｅｒｓ），第６巻、第１８３頁（１９７０年）に詳細な説明がある。また、レンガ積み会合体と同様な構造を持つ会合体として梯子または階段構造の会合体がある。梯子または階段構造の会合体については、Ｚｅｉｔｓｃｈｒｉｆｔ ｆｕｒ Ｐｈｙｓｉｋａｌｉｓｃｈｅ Ｃｈｅｍｉｅ，第４９巻、第３２４頁、（１９４１年）に詳細な説明がある。
【００４０】
また、レンガ積み会合体以外を形成するものとして、矢はず（Ｈｅｒｒｉｎｇｂｏｎｅ）構造をとる会合体（矢はず会合体と呼ぶことができる）などが知られている。
矢はず（Ｈｅｒｒｉｎｇｂｏｎｅ）会合体については、チャールズ・ライヒ（Ｃｈａｒｌｅｓ Ｒｅｉｃｈ）著、フォトグラフィック・サイエンス・アンド・エンジニアリング（Ｐｈｏｔｏｇｒａｐｈｉｃ Ｓｃｉｅｎｃｅ ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ）第１８巻、第３号、第３３５頁（１９７４年）に記載されている。矢はず会合体は、会合体に由来する２つの吸収極大を持つ。
【００４１】
会合状態を取っているかどうかは、前記の通りモノマー状態からの吸収（吸収λｍａｘ、ε、吸収形）の変化により確認することができる。
本発明の化合物は会合により短波長化（Ｈ会合）しても長波長化（Ｊ会合）してもその両方でもいずれでも良いが、Ｊ会合体を形成することがより好ましい。
【００４２】
化合物の分子間会合状態は様々な方法に形成することができる。
例えば溶液系では、ゼラチンのようなマトリックスを添加した水溶液（例えばゼラチン０．５ｗｔ％・化合物１０^−４Ｍ水溶液）、ＫＣｌのような塩を添加した水溶液（例えばＫＣｌ５％・化合物２×１０^−３Ｍ水溶液）に化合物を溶かす方法、良溶媒に化合物を溶かしておいて後から貧溶媒を加える方法（例えばＤＭＦ−水系、クロロホルム−トルエン系等）等が挙げられる。
また膜系では、ポリマー分散系、アモルファス系、結晶系、ＬＢ膜系等の方法が挙げられる。
さらに、バルクまたは微粒子（μｍ〜ｎｍサイズ）半導体（例えばハロゲン化銀、酸化チタン等）、バルクまたは微粒子金属（例えば金、銀、白金等）に吸着、化学結合、または自己組織化させることにより分子間会合状態を形成させることもできる。カラー銀塩写真における、ハロゲン化銀結晶上のシアニン色素Ｊ会合吸着による分光増感はこの技術を利用したものである。
分子間会合に関与する化合物数は２個であっても、非常に多くの化合物数であっても良い。
【００４３】
以下に、本発明で用いられる、非共鳴２光子吸収を行うことを特徴とするメロシアニン色素の好ましい具体例を挙げるが、本発明はこれらに限定されるものではない。
【００４４】
【化５】

【００４５】
【化６】

【００４６】
【化７】

【００４７】
【化８】

【００４８】
【実施例】
以下に、本発明の具体的な実施例について実験結果を基に説明する。勿論、本発明はこれらの実施例に限定されるものではない。
【００４９】
［実施例１］
［Ｄ−１４の合成］
【００５０】
本発明の化合物Ｄ−１４は以下の方法により合成することができる。
【００５１】
【化９】

【００５２】
４級塩［１］２．８１ｇ（１０ｍｍｏｌ）、［２］６．６７ｇ（３０ｍｍｏｌ）、無水酢酸１０ｇ、アセトニトリル５０ｍｌを３０分間還流した。濃縮後酢酸エチルでデカンテーションし、アニル体［３］の粗製品を得た。
アニル体［３］の粗製品にチオバルビツール酸［４］２．００ｇ（１０ｍｍｏｌ），トリエチルアミン３．０ｇ（３０ｍｍｏｌ）、エタノール１００ｍｌを加えて１時間還流した。濃縮後、シリカゲルカラムクロマトグラフィ（展開溶媒：クロロホルム：メタノール＝２０：１→１０：１）にて精製し、さらにメタノール−イソプロピルアルコールにて再結晶することにより、目的のＤ−１４の結晶２．５５ｇ（トータル収率４１．３％）を得た。
なお構造はＮＭＲスペクトル、ＭＳスペクトル、元素分析にて確認した。
【００５３】
また、他のメロシアニン色素等についても、Ｆ．Ｍ．Ｈａｒｍｅｒ著、Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃｏｍｐｏｕｎｄｓ−Ｃｙａｎｉｎｅ Ｄｙｅｓ ａｎｄ Ｒｅｌａｔｅｄ Ｃｏｍｐｏｕｎｄｓ、Ｊｏｈｎ＆Ｗｉｌｅｙ＆Ｓｏｎｓ、Ｎｅｗ Ｙｏｒｋ、Ｌｏｎｄｏｎ、１９６４年刊、Ｄ．Ｍ．Ｓｔｕｒｍｅｒ著、Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃｏｍｐｏｕｎｄｓ− Ｓｐｅｃｉａｌ Ｔｏｐｉｃｓ ｉｎ Ｈｅｔｅｒｏｃｙｃｌｉｃ Ｃｈｅｍｉｓｔｒｙ、第１８章、第１４節、第４８２から５１５頁、Ｊｏｈｎ＆Ｗｉｌｅｙ＆Ｓｏｎｓ、Ｎｅｗ Ｙｏｒｋ、Ｌｏｎｄｏｎ等に記載の方法等に準じて合成することができる。
ただし、本発明の化合物の合成法はこれに限定されるわけではない。
【００５４】
［実施例２］
［２光子吸収断面積の評価方法］
【００５５】
本発明の化合物の２光子吸収断面積の評価は、Ｍ． Ａ． Ａｌｂｏｔａ ｅｔ ａｌ．， Ａｐｐｌ． Ｏｐｔ． １９９８年，３７巻，７３５２頁．記載の方法を参考に行った。２光子吸収断面積測定用の光源には、Ｔｉ：ｓａｐｐｈｉｒｅパルスレーザー（パルス幅：１００ｆｓ、繰り返し：８０ＭＨｚ、平均出力：１Ｗ、ピークパワー：１００ｋＷ）を用い、７００ｎｍから１０００ｎｍの波長範囲で２光子吸収断面積を測定した。また、基準物質としてローダミンＢおよびフルオレセインを測定し、得られた測定値をＣ． Ｘｕ ｅｔ ａｌ．， Ｊ． Ｏｐｔ． Ｓｏｃ． Ａｍ． Ｂ １９９６年， １３巻， ４８１頁．に記載のローダミンＢおよびフルオレセインの２光子吸収断面積の値を用いて補正することで、各化合物の２光子吸収断面積を得た。２光子吸収測定用の試料には、１×１０^−４の濃度で化合物を溶かした溶液を用いた。
【００５６】
本発明の化合物の２光子吸収断面積を上記方法にて測定し、得られた結果をＧＭ単位で表１に示した（１ＧＭ ＝ １×１０^−５０ ｃｍ^４ ｓ ／ ｐｈｏｔｏｎ）。なお、表中に示した値は測定波長範囲内での２光子吸収断面積の最大値である。
【００５７】
さらに、下記に示した構造を有する、非特許文献８（Ｍ．Ａｌｂｏｔａ．ｅｔａｌ．，Ｓｃｉｅｎｃｅ．１９９８年，２８１巻，１６５３頁）記載の比較化合物１の２光子吸収断面積を上記の方法で測定し、結果を表１に示した。
【００５８】
【化１０】

【００５９】
【表１】

【００６０】
表１から明らかなように、本発明の化合物は比較化合物１に対し極めて大きい２光子吸収断面積が得られることがわかった。
【００６１】
［実施例３］
［２光子発光強度の評価方法］
【００６２】
実施例２の試料１０１に、Ｎｄ：ＹＡＧレーザーの１０６４ｎｍのレーザーパルスを照射して得られる発光スペクトルを測定し、得られた発光スペクトルの面積から非共鳴２光子発光強度を求めた。
【００６３】
比較試料１：強い２光子発光を発する化合物として国際公開第９７／０９０４３号（ＷＯ９７０９０４３）に記載の化合物（下記化合物）０．００５９ｇを１００ｍＬのアセトニトリルに溶解させて１×１０^−４Ｍの溶液を調製した。
【００６４】
【化１１】

【００６５】
試料１０１および比較試料１に、それぞれＮｄ：ＹＡＧレーザーの１０６４ｎｍのレーザーパルスを同条件で照射し、非共鳴２光子発光スペクトルを測定した。得られた発光スペクトルの面積（非共鳴２光子発光強度）を、比較試料１の値を１としたときの相対比で表２に示した。
【００６６】
【表２】

【００６７】
表２から明らかなように、比較化合物”ｄｙｅ１”に対しはるかに大きい非共鳴２光子発光強度が得られることがわかった。
【００６８】
【発明の効果】
本発明の非共鳴２光子吸収を行うことを特徴とするメロシアニン色素を用いることで、従来よりも強い非共鳴２光子吸収及び２光子発光を示す非共鳴２光子吸収発光材料を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a material that exhibits a nonlinear optical effect, and more particularly to an organic nonlinear optical material that has a large non-resonant two-photon absorption cross-section and a large luminous efficiency from an excited state generated by non-resonant two-photon absorption.
[0002]
[Prior art]
In general, the nonlinear optical effect is a non-linear optical response proportional to the square of the applied photoelectric field, the third power or more, and a second-order nonlinear optical effect proportional to the square of the applied photoelectric field. For example, second harmonic generation (SHG), optical rectification, photorefractive effect, Pockels effect, parametric amplification, parametric oscillation, optical sum frequency mixing, optical difference frequency mixing, and the like are known. The third-order nonlinear optical effect proportional to the cube of the applied photoelectric field includes third harmonic generation (THG), optical Kerr effect, self-induced refractive index change, two-photon absorption, and the like.
[0003]
Many inorganic materials have been found so far as nonlinear optical materials exhibiting these nonlinear optical effects. However, inorganic materials are very difficult to put into practical use because so-called molecular design for optimizing desired nonlinear optical characteristics and various physical properties necessary for device fabrication is difficult. On the other hand, organic compounds can be optimized not only for the desired nonlinear optical properties by molecular design, but also for other physical properties, so they are highly practical and attract attention as promising nonlinear optical materials. Collecting.
[0004]
In recent years, the third-order nonlinear optical effect has attracted attention among the nonlinear optical characteristics of organic compounds, and among these, non-resonant two-photon absorption and non-resonant two-photon emission have attracted attention. Two-photon absorption is a phenomenon in which a compound is excited by simultaneously absorbing two photons, and the case where two-photon absorption occurs in an energy region where there is no (linear) absorption band of the compound is called non-resonant two-photon absorption. . In addition, non-resonant two-photon emission refers to light emitted by an excited molecule generated by non-resonant two-photon absorption in the process of radiation deactivation in its excited state. In the following description, two-photon absorption and two-photon emission refer to non-resonant two-photon absorption and non-resonant two-photon emission, unless otherwise specified.
[0005]
By the way, the efficiency of non-resonant two-photon absorption is proportional to the square of the applied photoelectric field (square characteristic of two-photon absorption). For this reason, when a two-dimensional plane is irradiated with a laser, two-photon absorption occurs only at a position where the electric field strength is high in the central portion of the laser spot, and two-photon absorption is completely absent in a portion where the electric field strength is weak in the peripheral portion. Does not happen. On the other hand, in the three-dimensional space, two-photon absorption occurs only in the region where the electric field strength at the focal point where the laser light is collected by the lens is large, and no two-photon absorption occurs in the region outside the focal point because the electric field strength is weak. . Compared with linear absorption where excitation occurs at all positions in proportion to the intensity of the applied photoelectric field, non-resonant two-photon absorption results in excitation at only one point inside the space due to this square characteristic. , The spatial resolution is significantly improved. Usually, when inducing non-resonant two-photon absorption, a short-pulse laser in the near-infrared region, which is longer than the wavelength region in which the (linear) absorption band of the compound exists and does not have absorption, is often used. Because so-called transparent near-infrared light that does not have a (linear) absorption band of the compound is used, excitation light can reach the inside of the sample without being absorbed or scattered, and because of the square characteristic of non-resonant two-photon absorption In addition, since one point inside the sample can be excited with extremely high spatial resolution, non-resonant two-photon absorption and non-resonant two-photon emission are expected in applications such as two-photon contrast and two-photon photodynamic therapy (PDT) of biological tissues. ing. In addition, when non-resonant two-photon absorption and two-photon emission are used, a photon with an energy higher than the energy of the incident photon can be extracted. Therefore, research on upconversion lasing has been reported from the viewpoint of a wavelength conversion device.
[0006]
A so-called stilbazolium derivative is known as an organic compound that efficiently exhibits two-photon emission and upconversion lasing (He, GS et al., Appl. Phys. Lett. 1995, 67, 3703 [Non-patent Document 1]. He, GS et al., Appl. Phys. Lett. 1995, 67, 2433 [Non-Patent Document 2], He, GS et al., Appl. Phys. Lett. 1996, 68, 3549 [Non Patent Literature 3], He, GS et al., J. Appl. Phys. 1997, 81, 2529 [Non Patent Literature 4], Prasad, P. N. et al., Nonlinear Optics 1999, 21, 39 [Non-Patent Document 5], Ren, Y. et al., J. Mater. 00, 10, 2025 [Non-patent document 6], Zhou, G. et al., Jpn. J. Appl. Phys. 2001, 40, 1250 [Non-patent document 7], M. Albota. Et al., Science. 1998, 281, 1653 [Non-Patent Document 8]). Various application examples using two-photon emission of a stilbazolium compound having a specific structure are described in WO97 / 09043 [Patent Document 1].
[0007]
When non-resonant two-photon emission is used for imaging of biological tissue, photodynamic therapy, up-conversion lasing, etc., it is caused by the two-photon absorption efficiency (two-photon absorption cross section) and two-photon absorption of the organic compound used. The luminous efficiency from the excited state needs to be high. In order to obtain the doubled two-photon emission intensity using the same organic compound, the excitation light intensity of four times is required due to the square characteristic of the two-photon absorption. However, excessively strong laser light irradiation is not desirable because, for example, there is a high possibility that the biological tissue will be damaged by light, or that the two-photon luminescent dye itself will be photodegraded. Therefore, in order to obtain strong two-photon emission with weak excitation light intensity, it is necessary to develop an organic compound that efficiently absorbs two-photons and emits two-photon emission. The two-photon emission efficiency of the stilbazolium derivative is not yet sufficient for practical use.
[0008]
[Non-Patent Document 1]
He, G.G. S. et al. , Appl. Phys. Lett. 1995, 67, 3703 [Non-Patent Document 2]
He, G.G. S. et al. , Appl. Phys. Lett. 1995, 67, 2433 [Non-Patent Document 3]
He, G.G. S. et al. , Appl. Phys. Lett. 1996, 68, 3549 [Non-Patent Document 4]
He, G.G. S. et al. , J .; Appl. Phys. 1997, 81, 2529 [Non-Patent Document 5]
Prasad, P.A. N. et al. , Nonlinear Optics 1999, 21, 39 [Non-patent Document 6]
Ren, Y. et al. et al. , J .; Mater. Chem. 2000, 10, 2025 [Non-patent Document 7]
Zhou, G .; et al. , Jpn. J. et al. Appl. Phys. 2001, 40, 1250 [Non-patent Document 8]
M.M. Albota. et al. , Science. 1998, 281, 1653 [Patent Document 1]
International Publication No. 97/09043 Pamphlet [0009]
[Problems to be solved by the invention]
As described above, non-resonant two-photon absorption and non-resonant two-photon emission can be used for various applications characterized by extremely high spatial resolution. Since the two-photon absorption ability is low and the two-photon emission efficiency is poor, a very high-power laser is required as an excitation light source for inducing two-photon absorption and two-photon emission.
[0010]
An object of the present invention is to provide an organic material that efficiently absorbs two-photons, that is, an organic material having a large two-photon absorption cross section, and an organic material that exhibits two-photon emission with a large emission intensity.
[0011]
[Means for Solving the Problems]
As a result of intensive studies by the inventors, the above object of the present invention has been achieved by the following means.
(1) A non-resonant two-photon absorption material comprising a merocyanine dye that performs non-resonant two-photon absorption.
(2) The non-resonant two-photon absorption material according to (1), wherein the merocyanine dye is represented by the following general formula (1).
[0012]
[Chemical 3]

[0013]
In the general formula (1), Za ₃ represents an atomic group that forms a 5- or 6-membered nitrogen-containing heterocyclic ring, and Za ₄ represents an atomic group that forms a 5- or 6-membered ring.
Ra ₃ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Ma _{8 to} Ma ₁₁ each independently represent a methine group, may have a substituent, and may form a ring with another methine group. na ³ is 0 or 1, and ka ² represents an integer of 0 to 8. When ka ¹ is 2 or more, the plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.
CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.
(3) The non-resonant two-photon absorption material according to (2), wherein na ³ is 0 in (2).
(4) The non-resonant two-photon absorption material according to any one of (1) to (3), wherein the merocyanine dye is represented by the following general formula (2).
[0014]
[Formula 4]

[0015]
In General Formula (2), Ma ₁₀ , Ma ₁₁ , Ra ₃ , Za ₄ , ka ² , CI, and y are as defined in General Formula (1). X ₁ represents any of —O—, —S—, —NR ₃ —, —CR ₄ R ₅ —, and each of R ₃ , R ₄ , and R ₅ independently represents a hydrogen atom, an alkyl group, an alkenyl group, Represents an aryl group or a heterocyclic group.
R ₁ represents a substituent, and a 1 represents an integer of 0 to 4. When a1 is 2 or more, plural R ₁ may be the same or different, may form a ring.
(5) The non-resonant two-photon absorption material according to any one of (2) to (4), wherein ka ² is represented by 0 to 4 in (2) to (4).
(6) The non-resonant two-photon absorption material according to (5), wherein ka ² is represented by ² to 4 in (5).
(7) The non-resonant two-photon absorption material according to any one of (2) to (6), wherein Ra ₃ is an alkyl group in (2) to (6).
(8) The nonresonant two-photon absorption material according to any one of (4) to (7), wherein R ₃ , R ₄ , and R ₅ are all alkyl groups in (4) to (7).
(9) The non-resonant two-photon according to any one of (4) to (8), wherein, in (4) to (8), X ₁ is —O— or —CR ₄ R ₅ — Absorbing material.
(10) In (2) to (9), the ring formed from Za ₄ is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophene- Represented by 3-one, thiophen-3-one-1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione (2) The nonresonant two-photon absorption material according to any one of (2) to (9).
(11) In (10), the ring formed from Za ₄ is pyrazolidine-3,5-dione, indan-1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, The nonresonant two-photon absorption material according to (10), which is represented by 2-thiobarbituric acid.
(12) In (10), the ring formed from Za ₄ is represented by pyrazolidine-3,5-dione, barbituric acid, 2-thiobarbituric acid, Non-resonant two-photon absorption material.
(13) In (2) to (12), Ma ₁₀ and Ma ₁₁ are each represented by any one of an unsubstituted methine group, a methyl-substituted methine group, and an ethyl-substituted methine group. 12) The non-resonant two-photon absorption material according to any one of 12).
(14) A non-resonant two-photon light-emitting dye and a non-resonant two-photon light-emitting material comprising the non-resonant two-photon light-emitting dye according to (1) to (13), wherein the two-photon light-emitting dye emits two-photons.
(15) The two-photon absorption is induced by irradiating the non-resonant two-photon absorption dye described in (1) to (13) with a laser beam having a wavelength longer than the linear absorption band of the dye. Non-resonant two-photon absorption induction method.
(16) The non-resonant two-photon absorption dye described in (1) to (13) is irradiated with laser light having a wavelength longer than the linear absorption band of the dye to induce non-resonant two-photon absorption, thereby emitting light. A non-resonant two-photon emission generation method characterized by generating
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Below, the compound which performs non-resonant two-photon absorption of this invention is demonstrated in detail.
In the present invention, when a specific moiety is referred to as a “group”, unless otherwise specified, it may be substituted with one or more (up to the maximum possible) substituents. It means that it is not necessary. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention may be any substituent regardless of the presence or absence of substitution.
In the present invention, when a specific moiety is referred to as “ring”, or when “group” includes “ring”, it may be monocyclic or condensed unless otherwise specified. May not be substituted.
For example, the “aryl group” may be a phenyl group, a naphthyl group, or a substituted phenyl group.
[0017]
Here, the merocyanine dye that performs non-resonant two-photon absorption of the present invention will be described.
In addition, in this invention, a pigment | dye is a general term with respect to the compound which has a part of absorption in visible region (400-700 nm) and / or near-infrared region (700-2000 nm).
[0018]
Merocyanine dye is a general term for dyes in which both ends of a conjugated methine chain are an oxygen atom and a nitrogen atom. Specific examples of merocyanine dyes include F.I. M.M. Examples include those described in Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964.
[0019]
The merocyanine dye characterized by performing non-resonant two-photon absorption of the present invention is more preferably a merocyanine dye represented by the general formula (1).
[0020]
In the general formula (1), Za ₃ represents an atomic group forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring. The 5-membered or 6-membered nitrogen-containing heterocycle formed is preferably an oxazole nucleus having 3 to 25 carbon atoms (hereinafter referred to as C number) (for example, 2-3-methyloxazolyl, 2-3-ethyloxazolyl). , 2-3,4-diethyloxazolyl, 2-3-methylbenzoxazolyl, 2-3-ethylbenzoxazolyl, 2-3-sulfoethylbenzoxazolyl, 2-3-sulfopropyl Benzoxazolyl, 2-3-methylthioethylbenzoxazolyl, 2-3-methoxyethylbenzoxazolyl, 2-3-sulfobutylbenzoxazolyl, 2-3-methyl-β-naphthoxazolyl 2-3-methyl-α-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3-sulfopropyl-β-naphthoxazolyl, 2-3- ( -Naphthoxyethyl) benzoxazolyl, 2-3,5-dimethylbenzoxazolyl, 2-6-chloro-3-methylbenzoxazolyl, 2-5-bromo-3-methylbenzoxazolyl, 2- 3-ethyl-5-methoxybenzoxazolyl, 2-5-phenyl-3-sulfopropylbenzoxazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzoxazolyl, 2-3 -Dimethyl-5,6-dimethylthiobenzoxazolyl), thiazole nuclei having 3 to 25 carbon atoms (for example, 2-methylthiazolyl, 2-3-ethylthiazolyl, 2-3-sulfopropylthiazolyl, 2- 3-sulfobutylthiazolyl, 2-3,4-dimethylthiazolyl, 2-3,4,4-trimethylthiazolyl, 2-3-carboxyethylthiazolyl, 2 -3-methylbenzothiazolyl, 2-3-ethylbenzothiazolyl, 2-3-butylbenzothiazolyl, 2-3-sulfopropylbenzothiazolyl, 2-3-sulfobutylbenzothiazolyl , 2-3-methyl-β-naphthothiazolyl, 2-3-sulfopropyl-γ-naphthothiazolyl, 2-3- (1-naphthoxyethyl) benzothiazolyl, 2-3,5-dimethylbenzothiazolyl, 2-6-chloro -3-methylbenzothiazolyl, 2-6-iodo-3-ethylbenzothiazolyl, 2-5-bromo-3-methylbenzothiazolyl, 2-3-ethyl-5-methoxybenzothiazolyl 2-5-phenyl-3-sulfopropylbenzothiazolyl, 2-5- (4-bromophenyl) -3-sulfobutylbenzothiazolyl, 2-3-dimethyl-5,6- Dimethylthiobenzothiazolyl), imidazole nucleus having 3 to 25 carbon atoms (for example, 2-1,3-diethylimidazolyl, 2-1,3-dimethylimidazolyl, 2-1-methylbenzimidazolyl, 2- 1,3,4-triethylimidazolyl, 2-1,3-diethylbenzimidazolyl, 2-1,3,5-trimethylbenzimidazolyl, 2-6-chloro-1,3-dimethylbenzimidazolyl, 2-5,6-dichloro- 1,3-diethylbenzimidazolyl, 2-1,3-disulfopropyl-5-cyano-6-chlorobenzimidazolyl, etc.), C10-30 indolenine nucleus (for example, 3,3-dimethylindolenine) ), A quinoline nucleus having 9 to 25 carbon atoms (for example, 2-1-methylquinolyl, 2-1-ethylquinolyl) 2-1-methyl 6-chloroquinolyl, 2-1,3-diethylquinolyl, 2-1-methyl-6-methylthioquinolyl, 2-1-sulfopropylquinolyl, 4-1-methylquinolyl, 4-1 And sulfoethylquinolyl, 4-1-methyl-7-chloroquinolyl, 4-1,8-diethylquinolyl, 4-1-methyl-6-methylthioquinolyl, 4-1-sulfopropylquinolyl, etc.) , A C 3-25 selenazole nucleus (for example, 2-3methylbenzoselenazolyl etc.), a C 5-25 pyridine nucleus (for example, 2-pyridyl etc.) and the like can be mentioned. In addition, thiazoline nucleus, oxazoline nucleus, selenazoline nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole nucleus, imidazoline nucleus, imidazo [4,5-quino Zarin] nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, may be mentioned pyrimidine nucleus.
[0021]
These heterocyclic rings may be substituted, and the substituent is preferably, for example, an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl groups (preferably having 2 to 20 carbon atoms, such as vinyl, allyl, 2-butenyl, 1,3-butadienyl), cycloalkyl groups ( Preferably C 3-20, eg cyclopentyl, cyclohexyl), aryl group (preferably C 20-20, eg phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocycle A group (preferably having 1 to 20 carbon atoms such as pyridyl, thienyl, furyl, thiazolyl, Midazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, such as ethynyl, 2-propynyl, 1,3-butadiynyl, 2-phenylethynyl), halogen atom (for example, F, Cl Br, I), an amino group (preferably C 0-20, such as amino, dimethylamino, diethylamino, dibutylamino, anilino), cyano group, nitro group, hydroxyl group, mercapto group, carboxyl group, sulfo group, Phosphonic acid group, acyl group (preferably C 1-20, such as acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (preferably C 1-20, such as methoxy, butoxy, cyclohexyloxy), aryloxy group (Preferably C number 6-26, for example, phenoxy , 1-naphthoxy), alkylthio group (preferably C 1-20, for example, methylthio, ethylthio), arylthio group (preferably C6-20, eg, phenylthio, 4-chlorophenylthio), alkylsulfonyl group (preferably Has a C number of 1 to 20, for example, methanesulfonyl, butanesulfonyl), an arylsulfonyl group (preferably a C number of 6 to 20, for example, benzenesulfonyl, paratoluenesulfonyl), a sulfamoyl group (preferably a C number of 0 to 20, For example, sulfamoyl, N-methylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (preferably having 1 to 20 carbon atoms, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N-phenylcarbamoyl) An acylamino group (preferably C number 1-20, such as acetylamino, benzoylamino), imino group (preferably C number 2-20, such as phthalimino), acyloxy group (preferably C number 1-20, such as acetyloxy, benzoyloxy), alkoxycarbonyl A group (preferably having 2 to 20 carbon atoms, such as methoxycarbonyl, phenoxycarbonyl), a carbamoylamino group (preferably having 1 to 20 carbon atoms, such as carbamoylamino, N-methylcarbamoylamino, N-phenylcarbamoylamino). More preferably, they are an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, and an alkoxycarbonyl group.
[0022]
These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.
[0023]
The 5-membered or 6-membered nitrogen-containing heterocyclic ring formed by Za ₃ is more preferably an oxazole nucleus, an imidazole nucleus, a thiazole nucleus, or an indolenine ring, and further preferably an oxazole nucleus or an indolenine ring.
[0024]
Za ₄ represents an atomic group forming a 5-membered or 6-membered ring. The ring formed from Za ₄ is a moiety generally referred to as an acidic nucleus, and is defined by James, The Theory of the Photographic Process, 4th edition, McMillan, 1977, p. 198. Za ₄ is preferably 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline- 5-one, 2-thiooxazoline-2,4-dione, isorhodanine, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one Indoline-3-one, 2-oxoindazolium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, 3,4-dihydroisoquinolin-4-one, 1,3 -Dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, indazoline-2 One, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone include nuclei such pyrazolopyridone.
More preferably, the ring formed from Za ₄ is 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one- 1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, coumarin-2,4-dione, more preferably pyrazolidine-3,5-dione, Indan-1,3-dione, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, most preferably pyrazolidine-3,5-dione, barbituric acid, 2- Thiobarbituric acid.
[0025]
The ring formed from Za ₄ may be substituted (preferred examples of the substituent are the same as those of the substituent on Za ₃ ). More preferably, the substituent is preferably an alkyl group, an aryl group, a heterocyclic group, a halogen. An atom, a cyano group, a carboxyl group, a sulfo group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group.
[0026]
These heterocycles may be further condensed. Preferred examples of the condensed ring include a benzene ring, a benzofuran ring, a pyridine ring, a pyrrole ring, an indole ring, and a thiophene ring.
[0027]
Each of Ra ₃ independently represents a hydrogen atom or an alkyl group (preferably having a C number of 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4- Sulfobutyl, 3-methyl-3-sulfopropyl, 2′-sulfobenzyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C 2-20, for example, vinyl, allyl), aryl group (preferably C Formula 6-20, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), heterocyclic group (preferably C 1-20, for example, pyridyl, thienyl, furyl, thiazolyl, Imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), more preferably alkyl (Preferably an alkyl group having a C number of 1 to 6) or a sulfoalkyl group (preferably 3-sulfopropyl, 4-sulfobutyl, 3-methyl-3-sulfopropyl, 2'-sulfobenzyl).
[0028]
Ma _{8 to} Ma ₁₁ each represent a methine group and may have a substituent (examples of preferred substituents are the same as examples of substituents on Za ₃ and Za ₄ ), and the substituent is preferably an alkyl group , Halogen atom, nitro group, alkoxy group, aryl group, nitro group, heterocyclic group, aryloxy group, acylamino group, carbamoyl group, sulfo group, hydroxy group, carboxy group, alkylthio group, cyano group, etc. More preferably, it is an alkyl group.
Ma _{8 to} Ma ₁₁ are preferably unsubstituted methine groups or alkyl groups (preferably having a C number of 1 to 6) substituted methine groups, more preferably unsubstituted, ethyl group-substituted, and methyl group-substituted methine groups.
Ma _{8 to} Ma ₁₁ may be linked to each other to form a ring, and preferred examples of the ring formed include a cyclohexene ring, a cyclopentene ring, a benzene ring, and a thiophene ring.
[0029]
na ³ is 0 or 1, preferably 0.
[0030]
ka ² represents an integer of 0 to 8, preferably an integer of 0 to 4, more preferably 2 to 4, and even more preferably an integer of 2 or 3.
When ka ² is 2 or more, the plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.
[0031]
CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge.
[0032]
The merocyanine dye characterized by performing non-resonant two-photon absorption of the present invention is more preferably represented by the general formula (2).
[0033]
In General Formula (2), Ma ₁₀ , Ma ₁₁ , Ra ₃ , Za ₄ , ka ² , CI, and y are as defined in General Formula (1), and preferred ones are also the same.
[0034]
In General Formula (2), X ₁ represents any _one of —O—, —S—, —NR ₃ —, and —CR ₄ R ₅ —, and R ₃ , R ₄ , and R ₅ each independently represent a hydrogen atom. , An alkyl group, an alkenyl group, an aryl group, and a heterocyclic group (the preferred examples are the same as those for Ra ₃ ), and more preferably an alkyl group.
X ₁ is preferably —O— or —CR ₄ R ₅ —.
[0035]
R ₁ represents a substituent (examples of preferred substituents are the same as those of the substituent on Za ₃ ), and more preferably an alkyl group, aryl group, heterocyclic group, halogen atom, cyano group, carboxyl group, sulfo group. A group, an alkoxy group, a sulfamoyl group, a carbamoyl group, or an alkoxycarbonyl group.
[0036]
a1 represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.
When a1 is 2 or more, plural R ₁ may be the same or different, may be bonded to each other to form a ring, preferably a benzene ring as a ring formed, benzofuran ring, pyridine ring, pyrrole ring, indole Ring, thiophene ring and the like.
[0037]
The merocyanine dye of the present invention may be used in a monomer state or in an associated state.
Here, the dye chromophores are fixed in a specific spatial arrangement by a bond such as a covalent bond or a coordinate bond, or various intermolecular forces (hydrogen bond, van der Waals force, Coulomb force, etc.) This state is generally referred to as an association (or aggregation) state.
[0038]
For reference, the meeting is explained below. As for the association, for example, James, “The Theory of the Photographic Process”, 4th edition, Macmillan Publishing Company, 1977, Chapter 8, 218. Pp. 222 and “J-Aggregates” written by Takabayashi Kobayashi, World Scientific Publishing Co. Pte. Ltd., 1996). .
A monomer means a monomer. From the viewpoint of the absorption wavelength of the aggregate, the aggregate whose absorption shifts to a short wavelength with respect to monomer absorption is defined as an H aggregate (the dimer is specially called a dimer), and the aggregate whose shift is shifted to a long wavelength. Called coalescence.
[0039]
From the viewpoint of the structure of the aggregate, in a brick-stacked aggregate, when the deviation angle of the aggregate is small, it is called a J aggregate, but when the deviation angle is large, it is called an H aggregate. Brickwork aggregates are described in detail in Chemical Physics Letters, Vol. 6, page 183 (1970). In addition, as an aggregate having a structure similar to that of a brickwork aggregate, there is a ladder or staircase aggregate. Ladder or staircase structure aggregates are described in detail in Zeitschiff for Physikaliche Chemie, Vol. 49, p. 324 (1941).
[0040]
Moreover, as what forms other than a brickwork aggregate | assembly, the aggregate | assembly (it can call an arrowhead aggregate | assembly) etc. which take an arrow (Herringbone) structure etc. are known.
The Herringbone association is described in Charles Reich, Photographic Science and Engineering Vol. 18, No. 3, p. 335 (1974). Has been. The arrowhead aggregate has two absorption maxima derived from the aggregate.
[0041]
Whether or not it is in an associated state can be confirmed by a change in absorption (absorption λmax, ε, absorption type) from the monomer state as described above.
The compound of the present invention may be either short-wavelength (H-association) or long-wavelength (J-association) or both by association, but it is more preferable to form a J-aggregate.
[0042]
The intermolecular association state of a compound can be formed in various ways.
For example, in a solution system, an aqueous solution to which a matrix such as gelatin is added (for example, gelatin 0.5 wt% · compound 10 ⁻⁴ M aqueous solution), an aqueous solution to which a salt such as KCl is added (for example, KCl 5% · compound 2 × 10 ^−3). M aqueous solution), a method of dissolving a compound in a good solvent, a method of adding a poor solvent afterwards (for example, DMF-water system, chloroform-toluene system, etc.) and the like.
Examples of the film system include a polymer dispersion system, an amorphous system, a crystal system, and an LB film system.
Furthermore, molecules can be adsorbed, chemically bonded, or self-assembled into bulk or fine particle (μm to nm size) semiconductors (eg, silver halide, titanium oxide, etc.), bulk or fine particle metals (eg, gold, silver, platinum, etc.). Inter-association states can also be formed. Spectral sensitization by cyanine dye J-associative adsorption on silver halide crystals in a color silver salt photograph utilizes this technique.
The number of compounds involved in the intermolecular association may be two or a very large number of compounds.
[0043]
Hereinafter, preferred specific examples of the merocyanine dye used in the present invention and characterized by performing non-resonant two-photon absorption will be described, but the present invention is not limited thereto.
[0044]
[Chemical formula 5]

[0045]
[Chemical 6]

[0046]
[Chemical 7]

[0047]
[Chemical 8]

[0048]
【Example】
Hereinafter, specific embodiments of the present invention will be described based on experimental results. Of course, the present invention is not limited to these examples.
[0049]
[Example 1]
[Synthesis of D-14]
[0050]
Compound D-14 of the present invention can be synthesized by the following method.
[0051]
[Chemical 9]

[0052]
Quaternary salt [1] 2.81 g (10 mmol), [2] 6.67 g (30 mmol), acetic anhydride 10 g, and acetonitrile 50 ml were refluxed for 30 minutes. After concentration, it was decanted with ethyl acetate to obtain a crude product of anil [3].
To the crude product of the anil compound [3], 2.00 g (10 mmol) of thiobarbituric acid [4], 3.0 g (30 mmol) of triethylamine and 100 ml of ethanol were added and refluxed for 1 hour. After concentration, the residue was purified by silica gel column chromatography (developing solvent: chloroform: methanol = 20: 1 → 10: 1) and recrystallized from methanol-isopropyl alcohol to obtain 2.55 g of the desired D-14 crystal. (Total yield 41.3%) was obtained.
The structure was confirmed by NMR spectrum, MS spectrum and elemental analysis.
[0053]
Further, other merocyanine dyes and the like are also described in F.I. M.M. By Harmer, Heterocyclic Compounds-Cyanine Dies and Related Compounds, John & Wiley & Sons, New York, London, 1964, D.C. M.M. According to Sturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry, Chapter 18, Section 14, pages 482 to 515, according to John & Wiley & Sons, New Yor et al.
However, the synthesis method of the compound of the present invention is not limited to this.
[0054]
[Example 2]
[Method for evaluating two-photon absorption cross section]
[0055]
The evaluation of the two-photon absorption cross section of the compound of the present invention is described in M.M. A. Albota et al. , Appl. Opt. 1998, 37, 7352. The description was made with reference to the method described. A Ti: sapphire pulse laser (pulse width: 100 fs, repetition: 80 MHz, average output: 1 W, peak power: 100 kW) is used as a light source for measuring the two-photon absorption cross section, and two-photon absorption is performed in a wavelength range of 700 nm to 1000 nm. The cross-sectional area was measured. In addition, rhodamine B and fluorescein were measured as reference substances, and the obtained measured values were calculated as C.I. Xu et al. , J. et al. Opt. Soc. Am. B 1996, vol. 13, p. 481. Were corrected using the values of the two-photon absorption cross sections of rhodamine B and fluorescein described in 1. to obtain the two-photon absorption cross sections of the respective compounds. As a sample for two-photon absorption measurement, a solution in which a compound was dissolved at a concentration of 1 × 10 ⁻⁴ was used.
[0056]
The two-photon absorption cross-sectional area of the compound of the present invention was measured by the above method, and the results obtained are shown in Table 1 in GM units (1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s / photon). The value shown in the table is the maximum value of the two-photon absorption cross section within the measurement wavelength range.
[0057]
Furthermore, the two-photon absorption cross section of Comparative Compound 1 described in Non-Patent Document 8 (M. Albota. Et al., Science. 1998, 281, 1653) having the structure shown below was measured by the above method. The results are shown in Table 1.
[0058]
[Chemical Formula 10]

[0059]
[Table 1]

[0060]
As is apparent from Table 1, it was found that the compound of the present invention has a very large two-photon absorption cross section relative to Comparative Compound 1.
[0061]
[Example 3]
[Evaluation method of two-photon emission intensity]
[0062]
An emission spectrum obtained by irradiating the sample 101 of Example 2 with a 1064 nm laser pulse of an Nd: YAG laser was measured, and the non-resonant two-photon emission intensity was obtained from the area of the obtained emission spectrum.
[0063]
Comparative sample 1: 0.0059 g of the compound described in WO 97/09043 (WO9709043) (compound below) as a compound emitting strong two-photon emission was dissolved in 100 mL of acetonitrile to prepare a 1 × 10 ⁻⁴ M solution. Prepared.
[0064]
Embedded image

[0065]
Sample 101 and comparative sample 1 were each irradiated with a 1064 nm laser pulse of an Nd: YAG laser under the same conditions, and a non-resonant two-photon emission spectrum was measured. The area of the obtained emission spectrum (nonresonant two-photon emission intensity) is shown in Table 2 as a relative ratio when the value of Comparative Sample 1 is 1.
[0066]
[Table 2]

[0067]
As is clear from Table 2, it was found that a much higher non-resonant two-photon emission intensity was obtained for the comparative compound “dye1”.
[0068]
【The invention's effect】
By using the merocyanine dye characterized by performing non-resonant two-photon absorption of the present invention, a non-resonant two-photon absorbing light-emitting material exhibiting stronger non-resonant two-photon absorption and two-photon emission than before can be obtained.

Claims (9)

A non-resonant two-photon absorbing material comprising a merocyanine dye that performs non-resonant two-photon absorption. The non-resonant two-photon absorption material according to claim 1, wherein the merocyanine dye is represented by the following general formula (1).

In the general formula (1), Za ₃ represents an atomic group that forms a 5- or 6-membered nitrogen-containing heterocyclic ring, and Za ₄ represents an atomic group that forms a 5- or 6-membered ring.
Ra ₃ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.
Ma _{8 to} Ma ₁₁ each independently represent a methine group, may have a substituent, and may form a ring with another methine group. na ³ is 0 or 1, and ka ² represents an integer of 0 to 8. When ka ² is 2 or more, the plurality of Ma ₁₀ and Ma ₁₁ may be the same or different.
CI represents an ion for neutralizing the electric charge, and y represents a number necessary for neutralizing the electric charge. The non-resonant two-photon absorption material according to claim 2, wherein na ³ is 0 in claim 2. The non-resonant two-photon absorption material according to any one of claims 1 to 3, wherein the merocyanine dye is represented by the following general formula (2).

In General Formula (2), Ma ₁₀ , Ma ₁₁ , Ra ₃ , Za ₄ , ka ² , CI, and y are as defined in General Formula (1). X ₁ represents any of —O—, —S—, —NR ₃ —, —CR ₄ R ₅ —, and each of R ₃ , R ₄ , and R ₅ independently represents a hydrogen atom, an alkyl group, an alkenyl group, Represents an aryl group or a heterocyclic group.
R ₁ represents a substituent, and a 1 represents an integer of 0 to 4. When a1 is 2 or more, plural R ₁ may be the same or different, may form a ring. The non-resonant two-photon absorption material according to claim 2, wherein ka ² is represented by ² to 4 in claims 2 to 4. The ring formed from Za _{4 according} to any one of claims 2 to 5, wherein 2-pyrazolone-5-one, pyrazolidine-3,5-dione, rhodanine, indan-1,3-dione, thiophen-3-one, thiophene It is represented by -3-one-1,1-dioxide, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, or coumarin-2,4-dione. The nonresonant two-photon absorption material according to any one of claims 2 to 5. A nonresonant two-photon luminescent material, wherein the merocyanine dye that performs nonresonant two-photon absorption according to claim 1 emits two photons. The non-resonant characterized in that the merocyanine dye that performs non-resonant two-photon absorption according to claim 1 is irradiated with laser light having a wavelength longer than the linear absorption band of the dye to induce two-photon absorption. Two-photon absorption induction method. The merocyanine dye that performs non-resonant two-photon absorption according to claim 1 is irradiated with laser light having a wavelength longer than the linear absorption band of the dye to induce non-resonant two-photon absorption, thereby generating light emission. A method for generating non-resonant two-photon emission.