JP2004250545A - Nonresonant two-photon absorption material and nonresonant two-photon luminescent material, methods for inducing nonresonant two-photon absorption and luminescence using the materials, and methine compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic material which efficiently absorbs two photons, i.e. has a large two-photon absorption cross section. <P>SOLUTION: A nonresonant two-photon absorption material contains a compound of formula (1) or (2) (wherein R<SP>11</SP>-R<SP>16</SP>and R<SP>21</SP>-R<SP>24</SP>are each hydrogen atom or a substituent, some of which may be bound to each other to form a ring; m<SP>1</SP>and n<SP>1</SP>are each an integer of 0-4; R<SP>17</SP>and R<SP>25</SP>are each a substituent; i<SP>1</SP>and i<SP>2</SP>are each an integer of 0-4; X<SP>11</SP>and X<SP>12</SP>are identical to or different from each other and are each a (non)substituted aryl group or a (non)substituted heterocyclic group; m<SP>2</SP>and n<SP>2</SP>are each an integer of 1-4; R<SP>26</SP>and R<SP>27</SP>are each hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and Z<SP>21</SP>and Z<SP>22</SP>are each independently a group of atoms required for forming a 5- or 6-membered ring containing nitrogen). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１３】
式中Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６はそれぞれ独立に、水素原子、または置換基を表し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６のうちのいくつかが互いに結合して環を形成してもよい。ｍおよびｎはそれぞれ独立に０〜４の整数を表し、ｍ^１およびｎ^１が２以上の場合、複数個のＲ^１２、Ｒ^１３、Ｒ^１５およびＲ^１６は同一でもそれぞれ異なってもよい。Ｒ^１７は置換基を表し、ｉ^１は０以上４以下の整数を表す。ｉ^１が２以上の場合、複数個のＲ^１７は同一でもそれぞれ異なってもよい。Ｘ^１１およびＸ^１２は置換もしくは無置換のアリール基、または置換もしくは無置換のヘテロ環基を表し、同一でもそれぞれ異なってもよい。
一般式（２）
【００１４】
【化７】

【００１５】
式中、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４はそれぞれ独立に、水素原子、または置換基を表し、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４のうちのいくつかが互いに結合して環を形成してもよい。ｍ^２およびｎ^２はそれぞれ独立に１〜４の整数を表し、ｍ^２およびｎ^２ が２以上の場合、複数個のＲ^２１、Ｒ^２２、Ｒ^２３およびＲ^２４は同一でもそれぞれ異なってもよい。Ｒ^２５は置換基を表し、ｉ^２は０以上４以下の整数を表す。ｉ^２が２以上の場合、複数個のＲ^２５は同一でもそれぞれ異なってもよい。Ｒ^２６、Ｒ^２７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、またはヘテロ環基を表し、Ｚ^２１、Ｚ^２２はそれぞれ独立に５または６員環を形成する原子群を表す。
（２） 上記（１）に記載の一般式（１）または（２）で表される化合物を含むことを特徴とする非共鳴２光子発光材料。
（３） 上記（１）に記載の一般式（１）または（２）で表される化合物を含む非共鳴２光子吸収材料に、該化合物の有する線形吸収体よりも長波長のレーザー光を照射して非共鳴２光子吸収を誘起することを特徴とする非共鳴２光子吸収誘起方法。
（４） （２）に記載の一般式（１）または（２）で表される化合物を含む非共鳴２光子発光材料に、該化合物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、生成した励起状態から発光を発生させる非共鳴２光子発光発生方法。
（５） 一般式（３）または（５）で表されることを特徴とするメチン化合物。
一般式（３）
【００１６】
【化８】

【００１７】
式中Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６はそれぞれ独立に、水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６がアルキル基の場合、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６のうちのいくつかが互いに結合して環を形成してもよい。ｍ^３およびｎ^３はそれぞれ独立に０〜４の整数を表し、ｍ^３およびｎ^３が２以上の場合、複数個のＲ^３２、Ｒ^３３、Ｒ^３５およびＲ^３６は同一でもそれぞれ異なってもよい。Ｒ^３７は水素原子、アルキル基、またはアリール基を表し、ｉ^３は０以上４以下の整数を表す。ｉ^３が２以上の場合、複数個のＲ^３７は同一でもそれぞれ異なってもよい。Ｘ^３１およびＸ^３２は下記一般式（４）で表される基を表し、同一でもそれぞれ異なってもよい。
一般式（４）
【００１８】
【化９】

【００１９】
式中Ｒ^３８はヒドロキシ基、アルコキシ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、ジアリールアミノ基を表し、Ｒ^４０、Ｒ^４１はそれぞれ独立に、水素原子、ヒドロキシ基、アルコキシ基、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、またはジアリールアミノ基を表す。Ｒ^３９はアルキル基を表す。
一般式（５）
【００２０】
【化１０】

【００２１】
式中、Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４はそれぞれ独立に、水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４がアルキル基の場合、Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４のうちのいくつかが互いに結合して環を形成してもよい。ｍ^５およびｎ^５はそれぞれ独立に１〜４の整数を表し、ｍ^５およびｎ^５が２以上の場合、複数個のＲ^５１、Ｒ^５２、Ｒ^５３およびＲ^５４は同一でもそれぞれ異なってもよい。Ｒ^５５は水素原子、アルキル基、またはアリール基を表し、ｉ^５は０以上４以下の整数を表す。ｉ^５が２以上の場合、複数個のＲ^５５は同一でもそれぞれ異なってもよい。Ｒ^５６、Ｒ^５７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、またはヘテロ環基を表し、Ｚ^５１、Ｚ^５２はそれぞれ独立に５または６員環を形成する原子群を表す。
【００２２】
【発明の実施の形態】
以下に、上記一般式（１）および（２）で表される本発明の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。
【００２３】
一般式（１）において、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６はそれぞれ独立に、水素原子、または置換基を表し、置換基として好ましくは、アルキル基（好ましくは炭素数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（好ましくは炭素数２〜２０、例えば、ビニル、アリル）、シクロアルキル基（好ましくは炭素数３〜２０、例えばシクロペンチル、シクロヘキシル）、アリール基（好ましくは炭素数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）、アルコキシ基（好ましくは炭素数１〜１６、例えばメトキシ、エトキシ、ブトトキシ、シクロヘキシルオキシ）、アリールオキシ基（炭素数６〜１４、例えばフェノキシ、１‐ナフトキシ）、アミノ基（炭素数０〜２０、例えばジメチルアミノ、ジエチルアミノ、ジブチルアミノ）、ハロゲン原子、アルコキシカルボニル基（炭素数２〜１７、例えばメトキシカルボニル、エトキシカルボニル、ｔ−ブチルカルボニル）、カルバモイル基（炭素数１〜１０、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）、アシルアミノ基（炭素数１〜１０、ホルミルアミノ）、ヘテロ環基（好ましくは炭素数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）である。
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６としてより好ましくは水素原子またはアルキル基である。
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６のうちのいくつかが互いに結合して環を形成してもよく、環を形成する場合には、シクロヘキセン環、シクロペンテン環、ベンゼン環が好ましいが、
Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６はいずれも水素原子であることが好ましい。
【００２４】
一般式（１）において、ｍ^１およびｎ^１はそれぞれ独立に０〜４の整数を表し、好ましくは１〜３の整数を表す。なお、ｍ^１およびｎ^１が２以上の場合、複数個のＲ^１２、Ｒ^１３、Ｒ^１５およびＲ^１６は同一でもそれぞれ異なってもよい。
【００２５】
一般式（１）において、Ｒ^１７は置換基を表し、置換基として好ましくは上述のＲ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６で表される基の置換基として挙げた基を挙げることができる。
ｉ^１は０以上４以下の整数を表し、好ましくは０〜２の整数を表し、０が最も好ましい。ｉ^１が１以上の場合、複数個のＲ^１７は同一でもそれぞれ異なってもよい。
【００２６】
一般式（１）において、Ｘ^１１およびＸ^１２は置換もしくは無置換のアリール基、または置換もしくは無置換のヘテロ環基を表す。Ｘ^１１およびＸ^１２で表されるアリール基としては、フェニル、ナフチルアントラセニル、またはフェナンスレニル等を挙げることができ、フェニルまたはナフチルが好ましく、特にフェニルが好ましい。
【００２７】
一般式（１）においてＸ^１１およびＸ^１２で表されるヘテロ環基としては、炭素数１〜１５のヘテロ環基であり、更に好ましくは炭素数２〜１２のヘテロ環基であり、ヘテロ原子として好ましいものは、窒素原子、酸素原子または硫黄原子である。
ヘテロ環の具体例としては、例えばピロリジン、ピペリジン、ピペラジン、モルホリン、チオフェン、セレノフェン、フラン、ピロール、イミダゾール、ピラゾール、ピリジン、ピラジン、ピリダジン、ピリミジン、トリアゾール、トリアジン、インドール、インダゾール、プリン、チアゾリン、チアゾール、チアジゾール、オキサゾリン、オキサゾール、オキサジアゾール、キノリン、イソキノリン、フタラジン、ナフチリジン、キノキサリン、キナゾリン、シンノリン、プテリジン、アクリジン、フェナントロリン、フェナジン、テトラゾール、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、ベンゾトリアゾール、テトラザインデン、ベンゾインドレニン、カルバゾール、ジベンゾフラン、フェノチアジン、ジュロリジンおよび窒素原子が環を構成する場合には、その窒素原子が４級化された４級オニウムカチオン等が挙げられる。ヘテロ環として好ましくはピリジン、ピリミジン、ピラジン、インドール、チオフェン、チアゾール、オキサゾール、キノリン、アクリジン、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、ベンゾインドレニン、カルバゾール、フェノチアジン、ジュロリジンおよび窒素原子が環を構成する場合にその窒素原子が４級化された４級オニウムカチオン等であり、より好ましくは、カルバゾール、フェノチアジン、ジュロリジンである。ヘテロ環の結合位置はいずれでもよい。
【００２８】
一般式（１）のＸ^１１およびＸ^１２は更に置換基を有してもよく、該置換基として好ましくは上述のＲ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６で表される基の置換基として挙げた基を挙げることができる。
【００２９】
一般式（２）において、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４はそれぞれ独立に、水素原子または置換基を表し、置換基として好ましくは、アルキル基（好ましくは炭素数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（好ましくは炭素数２〜２０、例えば、ビニル、アリル）、シクロアルキル基（好ましくは炭素数３〜２０、例えばシクロペンチル、シクロヘキシル）、アリール基（好ましくは炭素数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）、アルコキシ基（好ましくは炭素数１〜１６、例えばメトキシ、エトキシ、ブトトキシ、シクロヘキシルオキシ）、アリールオキシ基（炭素数６〜１４、例えばフェノキシ、１‐ナフトキシ）、アミノ基（炭素数０〜２０、例えばジメチルアミノ、ジエチルアミノ、ジブチルアミノ）、ハロゲン原子、アルコキシカルボニル基（炭素数２〜１７、例えばメトキシカルボニル、エトキシカルボニル、ｔ−ブチルカルボニル）、カルバモイル基（炭素数１〜１０、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）、アシルアミノ基（炭素数１〜１０、ホルミルアミノ）、ヘテロ環基（好ましくは炭素数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）である。
Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４としてより好ましくは水素原子またはアルキル基である。
Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４のうちのいくつかが互いに結合して環を形成してもよいが、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４はいずれも水素原子であることが好ましい。
【００３０】
一般式（２）において、ｍ^２およびｎ^２はそれぞれ独立に１〜４の整数を表し、好ましくは１〜３の整数を表す。ｍ^２およびｎ^２が２以上の場合、複数個のＲ^２１、Ｒ^２２、Ｒ^２３およびＲ^２４は同一でもそれぞれ異なってもよい。
【００３１】
一般式（２）において、Ｒ^２６、Ｒ^２７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、またはヘテロ環基を表し（好ましい例はＲ^２１〜Ｒ^２４と同じ）、好ましくはアルキル基を表し、より好ましくは無置換アルキル基、またはスルホ基もしくはカルボキシル基が置換したアルキル基を表し、さらに好ましくは炭素数１〜６の無置換アルキル基または炭素数１〜４のスルホアルキル基を表す。
【００３２】
一般式（２）において、Ｚ^２１、Ｚ^２２はそれぞれ独立に５または６員環を形成する原子群を表す。形成されるヘテロ環として好ましくは、インドレニン環、アザインドレニン環、ピラゾリン環、ベンゾチアゾール環、チアゾール環、チアゾリン環、ベンゾオキサゾール環、オキサゾール環、オキサゾリン環、ベンゾイミダゾール環、イミダゾール環、チアジアゾール環、キノリン環、ピリジン環であり、より好ましくはインドレニン環、アザインドレニン環、ピラゾリン環、ベンゾチアゾール環、チアゾール環、チアゾリン環、チアジアゾール環、キノリン環であり、特に好ましくは、インドレニン環、アザインドレニン環である。
【００３３】
一般式（２）において、Ｚ^２１、Ｚ^２２により形成されるヘテロ環は置換基を有しても良く、置換基として好ましくは、アルキル基（好ましくは炭素数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（好ましくは炭素数２〜２０、例えば、ビニル、アリル）、シクロアルキル基（好ましくは炭素数３〜２０、例えばシクロペンチル、シクロヘキシル）、アリール基（好ましくは炭素数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（好ましくは炭素数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（好ましくは炭素数２〜２０、例えば、エチニル、２−メチルエチニル、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（好ましくは炭素数１〜２０、例えば、ジメチルアミノ、ジエチルアミノ、ジブチルアミノ）、シアノ基、ヒドロキシル基、カルボキシル基、スルホ基、アシル基（好ましくは炭素数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（好ましくは炭素数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（好ましくは炭素数６〜２６、例えば、フェノキシ、１−ナフトキシ）、アルキルチオ基（好ましくは炭素数１〜２０、例えば、メチルチオ、エチルチオ）、アリールチオ基（好ましくは炭素数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（好ましくは炭素数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（好ましくは炭素数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）、カルバモイル基（好ましくは炭素数１〜２０、例えば、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（好ましくは炭素数１〜２０、例えばアセチルアミノ、ベンゾイルアミノ）、イミノ基（好ましくは炭素数２〜２０、例えばフタルイミノ）、アシルオキシ基（好ましくは炭素数１〜２０、例えばアセチルオキシ、ベンゾイルオキシ）、またはアルコキシカルボニル基（好ましくは炭素数２〜２０、例えば、メトキシカルボニル、フェノキシカルボニル）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、カルボキシル基（その塩も含む）、スルホ基（その塩も含む）、アルコキシ基、カルバモイル基、またはアルコキシカルボニル基である。
【００３４】
一般式（１）で表される化合物の１つの好ましい形は一般式（３）で表される。一般式（３）において、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６はそれぞれ独立に、水素原子、アルキル基（好ましくは炭素数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）、アリール基（好ましくは炭素数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）またはハロゲン原子を表す。
Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６としてより好ましくは水素原子またはアルキル基である。
Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６のうちのいくつかが互いに結合して環を形成してもよく、環を形成する場合には、シクロヘキセン環、シクロペンテン環、ベンゼン環が好ましいが、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６はいずれも水素原子であることが好ましい。
【００３５】
一般式（３）において、ｍ^３およびｎ^３はそれぞれ独立に０〜４の整数を表し、好ましくは１〜３の整数を表す。なお、ｍ^３およびｎ^３が２以上の場合、複数個のＲ^３２、Ｒ^３３、Ｒ^３５およびＲ^３６は同一でもそれぞれ異なってもよい。
【００３６】
一般式（３）において、Ｒ^３７は水素原子、アルキル基、アリール基を表す。
ｉ^３は０以上４以下の整数を表し、好ましくは０〜２の整数を表し、０が最も好ましい。ｉ^３が１以上の場合、複数個のＲ^３７は同一でもそれぞれ異なってもよい。
【００３７】
一般式（３）において、Ｘ^３１およびＸ^３２は下記一般式（４）で表される基を表し、同一でもそれぞれ異なってもよい。
一般式（４）
【００３８】
【化１１】

【００３９】
一般式（４）において、Ｒ^３８はヒドロキシ基、アルコキシ基（好ましくは炭素数１〜１６、例えばメトキシ、エトキシ、ブトトキシ、シクロヘキシルオキシ）、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、またはジアリールアミノ基を表す。Ｒ^４０、Ｒ^４１はそれぞれ独立に、水素原子、ヒドロキシ基、アルコキシ基（好ましくは炭素数１〜１６、例えばメトキシ、エトキシ、ブトトキシ、シクロヘキシルオキシ）、アルキルアミノ基、ジアルキルアミノ基、アリールアミノ基、またはジアリールアミノ基を表す。Ｒ^３８は好ましくはジアルキルアミノ基、またはジアリールアミノ基である。Ｒ^４０、Ｒ^４１はそれぞれ水素原子である場合が好ましい。
【００４０】
一般式（４）においＲ^３９はアルキル基（好ましくは炭素数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）を表す。
【００４１】
一般式（２）で表される化合物の１つの好ましい形は一般式（５）で表される。一般式（５）において、Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４はそれぞれ独立に、水素原子、アルキル基（好ましくは炭素数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）、アリール基（好ましくは炭素数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）またはハロゲン原子を表す。
Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４としてより好ましくは水素原子またはアルキル基である。
Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４のうちのいくつかが互いに結合して環を形成してもよいが、Ｒ^５１、Ｒ^５２、Ｒ^５３、Ｒ^５４はいずれも水素原子であることが好ましい。
【００４２】
一般式（５）において、ｍ^５およびｎ^５はそれぞれ独立に１〜４の整数を表し、好ましくは１〜３の整数を表す。ｍ^５およびｎ^５が２以上の場合、複数個のＲ^５１、Ｒ^５２、Ｒ^５３およびＲ^５４は同一でもそれぞれ異なってもよい。
【００４３】
一般式（５）において、Ｒ^５６、Ｒ^５７はそれぞれ独立に水素原子、アルキル基またはアリール基を表し（好ましい例はＲ^５１〜Ｒ^５４と同じ）、好ましくはアルキル基を表し、より好ましくは無置換アルキル基、またはスルホ基もしくはカルボキシル基が置換したアルキル基を表し、さらに好ましくは炭素数１〜６の無置換アルキル基または炭素数１〜４のスルホアルキル基を表す。
【００４４】
一般式（５）において、Ｚ^５１、Ｚ^５２はそれぞれ独立に５または６員環を形成する原子群を表す。形成されるヘテロ環として好ましくは、インドレニン環、アザインドレニン環、ピラゾリン環、ベンゾチアゾール環、チアゾール環、チアゾリン環、ベンゾオキサゾール環、オキサゾール環、オキサゾリン環、ベンゾイミダゾール環、イミダゾール環、チアジアゾール環、キノリン環、ピリジン環であり、より好ましくはインドレニン環、アザインドレニン環、ピラゾリン環、ベンゾチアゾール環、チアゾール環、チアゾリン環、チアジアゾール環、キノリン環であり、特に好ましくは、インドレニン環、アザインドレニン環である。
【００４５】
一般式（５）において、Ｚ^５１、Ｚ^５２により形成されるヘテロ環は置換基を有しても良く、置換基として好ましくは、アルキル基（好ましくは炭素数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（好ましくは炭素数２〜２０、例えば、ビニル、アリル）、シクロアルキル基（好ましくは炭素数３〜２０、例えばシクロペンチル、シクロヘキシル）、アリール基（好ましくは炭素数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（好ましくは炭素数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（好ましくは炭素数２〜２０、例えば、エチニル、２−メチルエチニル、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（好ましくは炭素数１〜２０、例えば、ジメチルアミノ、ジエチルアミノ、ジブチルアミノ）、シアノ基、ヒドロキシル基、カルボキシル基、スルホ基、アシル基（好ましくは炭素数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（好ましくは炭素数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（好ましくは炭素数６〜２６、例えば、フェノキシ、１−ナフトキシ）、アルキルチオ基（好ましくは炭素数１〜２０、例えば、メチルチオ、エチルチオ）、アリールチオ基（好ましくは炭素数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（好ましくは炭素数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（好ましくは炭素数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）、カルバモイル基（好ましくは炭素数１〜２０、例えば、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（好ましくは炭素数１〜２０、例えばアセチルアミノ、ベンゾイルアミノ）、イミノ基（好ましくは炭素数２〜２０、例えばフタルイミノ）、アシルオキシ基（好ましくは炭素数１〜２０、例えばアセチルオキシ、ベンゾイルオキシ）、またはアルコキシカルボニル基（好ましくは炭素数２〜２０、例えば、メトキシカルボニル、フェノキシカルボニル）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、カルボキシル基（その塩も含む）、スルホ基（その塩も含む）、アルコキシ基、カルバモイル基、またはアルコキシカルボニル基であり、さらに好ましくは、アルキル基、アリール基、カルボキシル基（その塩も含む）、スルホ基（その塩も含む）、またはカルバモイル基である。
【００４６】
以下に、本発明で用いられる、一般式（１）または（２）で表される２光子吸収材料および非共鳴２光子発光材料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。
【００４７】
【化１２】

【００４８】
【化１３】

【００４９】
【化１４】

【００５０】
【化１５】

【００５１】
本発明の非共鳴２光子吸収材料および非共鳴２光子発光材料の用途としては、前出の特許文献１やＢａｈａｗａｌｋａｒ，Ｊ．Ｄ．ｅｔ ａｌ．，Ｒｅｐ．Ｐｒｏｇ．Ｐｈｙｓ．１９９６年，５９巻，１０４１頁に示されているように、赤外線検出方法、赤外レーザー光の強度分布検出方法、赤外光から目を保護するための眼鏡、赤外光を可視光に変換する波長変換器、オプティカルリミッテング、一重項酸素発生方法、細胞等の造影、ＰＤＴ、アップコンバージョンレーザー、マイクロファブリケーション、３次元光記録媒体が挙げられる。本発明の非共鳴２光子吸収材料および非共鳴２光子発光材料は特に細胞造影、ＰＤＴ、オプティカルリミッテング、マイクロファブリケーション、３次元光記録媒体に有効である。
【００５２】
【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。
【００５３】
［実施例１］
［Ａ−１の合成］
【００５４】
本発明の化合物Ａ−１は以下の方法により合成することができる。
また、本発明の他の化合物についても反応に用いる原料を変更することによりＡ−１の合成法と同様にし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。
【００５５】
【化１６】

【００５６】
原料化合物である４−シクロヘプテン−１−オン（１）はＤｏｎａｌｄ Ｊ． Ｍａｒｑｕａｒｄｔら著、Ｓｙｎｔｈｅｔｉｃ Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ誌、第１８巻、１１９３頁、１９８８年記載の方法により合成した。
【００５７】
４−シクロヘプテン−１−オン（１） ６．６ｇ（６０ｍｍｏｌ）をジクロロメタン５０ｍｌに溶解し、−７０℃、窒素雰囲気下で攪拌しながらＣａＣＯ_３ １．５ｇを添加し、続いてＢｒ_２ １０ｇ（６２．６ｍｍｏｌ）をゆっくりと滴下した。そのまま１時間攪拌を続けた後、室温まで温度を上げ、さらに４０分間攪拌を続けた。反応溶液に重曹水を加え、ジクロロメタンで抽出したのち、有機層をＭｇＳＯ_４にて乾燥、続いて有機層を濃縮して得られた固体をシクロヘキサンより再結晶して４，５−ジブロモシクロヘキサノン（２）の無色固体 ９．１ｇ（収率：５６％）を得た。
【００５８】
４，５−ジブロモシクロヘキサノン（２） ６．５ｇ（３７ｍｍｏｌ）とＮ，Ｎ−ジメチルアミノシンナムアルデヒド ５．０ｇ（１８．５ｍｍｏｌ）をメタノール性ＨＣｌ １００ｍｌに溶解させ、窒素雰囲気下、７０℃で５時間攪拌した。反応溶液に重曹水を加え、ジクロロメタンにより抽出、有機層をＭｇＳＯ_４にて乾燥後、濃縮して赤色結晶を得た。得られた粗結晶を酢酸エチルに懸濁させ、１５分程度還流した後ろ過して化合物３の橙色結晶 ６．５ｇ（収率：６０％）を得た。
【００５９】
化合物３ ０．９ｇ（１．５４ｍｍｏｌ）を脱水ＴＨＦ（１００ｍｌ）に懸濁させ、窒素雰囲気下、室温で攪拌しながら１，８−ジアザビシクロ［５，４，０］−７−ウンデセン（ＤＢＵ） ０．４７ｇ（３．１ｍｍｏｌ）を滴下し、１時間攪拌した。さらにＤＢＵ １．０ｇ（６．６ｍｍｏｌ ）を加え１時間攪拌したのち再びＤＢＵ １．０ｇ（６．６ｍｍｏｌ）を加えた。この操作を２回繰り返した後、反応溶液を４０℃に加温しながら１時間攪拌し、放冷後析出した褐色固体をろ別し、得られたろ液を塩水／ジクロロメタンで抽出した。有機層はＭｇＳＯ_４で乾燥した後、濃縮して黒色粗結晶を得た。得られた粗結晶はシリカゲルカラムクロマトグラフィーにより精製し（展開溶媒；クロロホルム：ヘキサン＝３：１）、本発明の化合物Ａ−１の濃紫色結晶 ０．４１ｇ（収率：６２％）を得た。
^１Ｈ ＮＭＲスペクトル（溶媒：Ｃｈｌｏｒｏｆｏｒｍ−ｄ^３）： ３．０２（ｓ， １２Ｈ）， ６．０７（ｄ， ２Ｈ）， ６．６７（ｄ， ４Ｈ）， ６．７１（ｄ， ２Ｈ）， ６．９６（ｄ， ２Ｈ）， ７．１４（ｔ， ２Ｈ）， ７．４２（ｄ， ４Ｈ）， ７．５１（ｄ， ２Ｈ）
【００６０】
［実施例２］
［２光子吸収断面積の評価方法］
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， ３７，７３５２．記載の方法を参考に行った。この測定法は、非共鳴２光子吸収が起こることにより誘起された励起状態からの発光の強度を、基準物質と被測定物質との間で比較する方法であり、２光子発光を起こす化合物でなければ測定できないが、他の方法に比べて簡便で比較的正確な値が得られるのが特徴である。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， １３， ４８１．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^−３の濃度でクロロホルムに化合物を溶かした溶液を用いた。
【００６１】
本発明の化合物Ａ−１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単位で下記に示した（１ＧＭ ＝ １×１０^−５０ ｃｍ^４ ｓ ／ ｐｈｏｔｏｎ）。なお、下記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。ベンジルアルコールを溶媒に用いた以外は同様にして測定した下記比較化合物の２光子吸収断面積も示した。
【００６２】
【化１７】

【００６３】
上に示したように、本発明により従来の材料をはるかに陵駕する良好な非共鳴２光子吸収／発光特性が得られた。
【００６４】
【発明の効果】
本発明の化合物を用いることにより、従来よりもはるかに効率よく非共鳴２光子吸収および発光を行う材料を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a material that exhibits a nonlinear optical effect, and particularly uses an organic nonlinear optical material having a large non-resonant two-photon absorption cross-section and a large emission efficiency from an excited state generated by non-resonant two-photon absorption, and the material. The present invention relates to a non-resonant two-photon absorption induction method or a non-resonant two-photon emission generation method. Furthermore, it is related with the novel methine compound suitable for these.
[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, respectively, 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 (Non-Patent Document 1, Non-Patent Document 2, Non-Patent Document 3, Non-Patent Document 4, Non-Patent Document 5, Non-Patent Document 5, Non-Patent Document 5, (See Patent Literature 6 and Non-Patent Literature 7). Various application examples using two-photon emission of a stilbazolium compound having a specific structure are described in Patent Document 1.
[0007]
[Non-Patent Document 1]
He, G.G. S. etal. , 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 [Patent Document 1]
WO 97/09043 Pamphlet [0008]
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.
[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. Another object is to provide a suitable non-resonant two-photon absorption inducing method or non-resonant two-photon emission generating method using the organic material. Moreover, it is providing the novel compound suitable for these materials and methods.
[0011]
[Means for Solving the Problems]
As a result of intensive studies by the inventors of the present invention, the above object of the present invention has been achieved by the following means.
(1) A non-resonant two-photon absorption material comprising a compound represented by the following general formula (1) or (2).
General formula (1)
[0012]
[Chemical 6]

[0013]
In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ each independently represents a hydrogen atom or a substituent, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ Some of them may combine with each other to form a ring. m and n each independently represents an integer of 0 to 4, and when m ¹ and n ¹ are 2 or more, a plurality of R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ may be the same or different. R ¹⁷ represents a substituent, and i ¹ represents an integer of 0 or more and 4 or less. When i ¹ is 2 or more, the plurality of R ¹⁷ may be the same or different. X ¹¹ and X ¹² represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and may be the same or different.
General formula (2)
[0014]
[Chemical 7]

[0015]
In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a substituent, and some of R ²¹ , R ²² , R ²³ , and R ²⁴ are bonded to each other to form a ring. May be formed. m ² and n ² each independently represent an integer of 1 to 4, and when m ² and n ² are 2 or more, a plurality of R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different. . R ²⁵ represents a substituent, and i ² represents an integer of 0 or more and 4 or less. If i ² is 2 or more, plural R ²⁵ may be the same or different. R ²⁶ and R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ²¹ and Z ²² each independently represent an atomic group that forms a 5- or 6-membered ring.
(2) A non-resonant two-photon light-emitting material comprising the compound represented by the general formula (1) or (2) described in (1) above.
(3) Irradiating a non-resonant two-photon absorption material containing the compound represented by the general formula (1) or (2) described in (1) above with a laser beam having a longer wavelength than the linear absorber of the compound Then, the non-resonant two-photon absorption induction method is induced.
(4) A non-resonant two-photon light-emitting material containing the compound represented by the general formula (1) or (2) described in (2) is irradiated with laser light having a wavelength longer than the linear absorption band of the compound. A non-resonant two-photon emission generation method that induces non-resonant two-photon absorption and generates light emission from the generated excited state.
(5) A methine compound represented by the general formula (3) or (5).
General formula (3)
[0016]
[Chemical 8]

[0017]
In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ³¹ , R ³² , R ³³ , R ³⁴ , When R ³⁵ and R ³⁶ are alkyl groups, some of R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ may be bonded to each other to form a ring. m ³ and n ³ each independently represents an integer of 0 to 4, and when m ³ and n ³ are 2 or more, a plurality of R ³² , R ³³ , R ³⁵ and R ³⁶ may be the same or different. . R ³⁷ represents a hydrogen atom, an alkyl group, or an aryl group, and i ³ represents an integer of 0 or more and 4 or less. When i ³ is 2 or more, the plurality of R ³⁷ may be the same or different. X ³¹ and X ³² represent a group represented by the following general formula (4), and may be the same or different.
General formula (4)
[0018]
[Chemical 9]

[0019]
In the formula, R ³⁸ represents a hydroxy group, an alkoxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group, and R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, a hydroxy group, an alkoxy group, an alkylamino group. Represents a group, a dialkylamino group, an arylamino group, or a diarylamino group. R ³⁹ represents an alkyl group.
General formula (5)
[0020]
[Chemical Formula 10]

[0021]
In the formula, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and when R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are an alkyl group, Some of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring. m ⁵ and n ⁵ each independently represent an integer of 1 to 4, and when m ⁵ and n ⁵ are 2 or more, a plurality of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different. . R ⁵⁵ represents a hydrogen atom, an alkyl group, or an aryl group, and i ⁵ represents an integer of 0 or more and 4 or less. When i ⁵ is 2 or more, the plurality of R ⁵⁵ may be the same or different. R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ⁵¹ and Z ⁵² each independently represent an atomic group that forms a 5- or 6-membered ring.
[0022]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the compounds of the present invention represented by the general formulas (1) and (2) will be described 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.
[0023]
In the general formula (1), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ each independently represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably a carbon Number 1 to 20, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), alkenyl group (preferably C2-C20, for example vinyl, allyl), cycloalkyl groups (preferably C3-C20, for example cyclopentyl, cyclohexyl), aryl groups (preferably C6-C20, for example phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), alkoxy group (preferably carbon 1 to 16, such as methoxy, ethoxy, butoxy, cyclohexyloxy), aryloxy group (having 6 to 14 carbon atoms, such as phenoxy, 1-naphthoxy), amino group (having 0 to 20 carbon atoms, such as dimethylamino, diethylamino, dibutyl) Amino), halogen atom, alkoxycarbonyl group (carbon number 2 to 17, for example, methoxycarbonyl, ethoxycarbonyl, t-butylcarbonyl), carbamoyl group (carbon number 1 to 10, for example, carbamoyl, N-methylcarbamoyl, N, N- Dimethylcarbamoyl), acylamino group (1-10 carbon atoms, formylamino), heterocyclic group (preferably 1-20 carbon atoms such as pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino) is there.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are more preferably a hydrogen atom or an alkyl group.
Some of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ may be bonded to each other to form a ring, and in the case of forming a ring, a cyclohexene ring, a cyclopentene ring, benzene A ring is preferred,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are all preferably hydrogen atoms.
[0024]
In the general formula (1), m ¹ and n ¹ each independently represents an integer of 0 to 4, preferably an integer of 1 to 3. When m ¹ and n ¹ are 2 or more, a plurality of R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ may be the same or different.
[0025]
In the general formula (1), R ¹⁷ represents a substituent, and the substituent is preferably exemplified as the substituent of the group represented by the above R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ . The group can be mentioned.
i ¹ represents an integer of 0 to 4, preferably an integer of 0 to 2, and most preferably 0. When i ¹ is 1 or more, the plurality of R ¹⁷ may be the same or different.
[0026]
In the general formula (1), X ¹¹ and X ¹² represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group. Examples of the aryl group represented by X ¹¹ and X ¹² include phenyl, naphthylanthracenyl, or phenanthrenyl, and phenyl or naphthyl is preferable, and phenyl is particularly preferable.
[0027]
In the general formula (1), the heterocyclic group represented by X ¹¹ and X ¹² is a heterocyclic group having 1 to 15 carbon atoms, more preferably a heterocyclic group having 2 to 12 carbon atoms, and a hetero atom Preferred as is a nitrogen atom, an oxygen atom or a sulfur atom.
Specific examples of the heterocyclic ring include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, selenophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, triazole, triazine, indole, indazole, purine, thiazoline, thiazole. , Thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, tetrazaindene , Benzoindolenin, carbazole, dibenzofuran, phenothiazine, julolidi And when the nitrogen atom constituting the ring, quaternary onium cations such as the nitrogen atom is quaternized, and the like. As a heterocyclic ring, preferably pyridine, pyrimidine, pyrazine, indole, thiophene, thiazole, oxazole, quinoline, acridine, benzimidazole, benzoxazole, benzothiazole, benzoindolenin, carbazole, phenothiazine, julolidine, and a nitrogen atom form a ring A quaternary onium cation in which the nitrogen atom is quaternized, and more preferably carbazole, phenothiazine, and julolidine. The bonding position of the heterocycle may be any.
[0028]
X ¹¹ and X ^{12 in} the general formula (1) may further have a substituent, and the substituent is preferably represented by the above-described R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ^16. Examples thereof include the groups listed as substituents of the group.
[0029]
In the general formula (2), R ²¹ , R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (preferably having 1 to 20 carbon atoms, for example, Methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms, for example, , Vinyl, allyl), cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3- Methylphenyl, 1-naphthyl), alkoxy group (preferably having 1 to 16 carbon atoms, eg, Toxi, ethoxy, butoxy, cyclohexyloxy), aryloxy groups (C6-C14, such as phenoxy, 1-naphthoxy), amino groups (C0-20, such as dimethylamino, diethylamino, dibutylamino), halogen atoms, Alkoxycarbonyl group (C2-17, such as methoxycarbonyl, ethoxycarbonyl, t-butylcarbonyl), carbamoyl group (C1-10, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl), acylamino group (C1-C10, formylamino), a heterocyclic group (preferably C1-C20, for example, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino).
R ²¹ , R ²² , R ²³ and R ²⁴ are more preferably a hydrogen atom or an alkyl group.
Some of R ²¹ , R ²² , R ²³ , and R ²⁴ may be bonded to each other to form a ring, but R ²¹ , R ²² , R ²³ , and R ²⁴ may all be hydrogen atoms. preferable.
[0030]
In the general formula (2), ^{m 2} and ^{n 2} each independently represents an integer of 1 to 4, preferably an integer of 1-3. When m ² and n ² are 2 or more, a plurality of R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different.
[0031]
In the general formula (2), R ²⁶ and R ²⁷ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group (preferred examples are the same as those of R ^{21 to} R ²⁴ ), preferably an alkyl group Represents a group, more preferably an unsubstituted alkyl group, or an alkyl group substituted with a sulfo group or a carboxyl group, more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms or a sulfoalkyl group having 1 to 4 carbon atoms. Represent.
[0032]
In the general formula (2), Z ²¹ and Z ²² each independently represent an atomic group forming a 5- or 6-membered ring. The heterocycle formed is preferably an indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, imidazole ring, thiadiazole ring Quinoline ring, pyridine ring, more preferably indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, thiadiazole ring, quinoline ring, particularly preferably indolenine ring, It is an azaindolenine ring.
[0033]
In the general formula (2), the heterocycle formed by Z ²¹ and Z ²² may have a substituent, and the substituent is preferably an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl , N-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms such as vinyl, Allyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, for example, pyridyl, thienyl Furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, for example, ethynyl, 2-methylethynyl, 2-phenylethynyl), halogen atom (for example, F, Cl, Br, I), an amino group (preferably having 1 to 20 carbon atoms, for example, dimethylamino, diethylamino, dibutylamino), cyano group, hydroxyl group, carboxyl group, sulfo group, acyl group (preferably having 1 to 20 carbon atoms, For example, acetyl, benzoyl, salicyloyl, pivaloyl), an alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy, butoxy, cyclohexyloxy), an aryloxy group (preferably having 6 to 26 carbon atoms, such as phenoxy, 1- Naphthoxy), alkylthio group (preferably Or an arylthio group (preferably 6-20 carbons such as phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (preferably 1-20 carbons such as, for example, Methanesulfonyl, butanesulfonyl), arylsulfonyl groups (preferably having 6 to 20 carbon atoms, such as benzenesulfonyl, paratoluenesulfonyl), carbamoyl groups (preferably having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (preferably having 1 to 20 carbon atoms, such as acetylamino, benzoylamino), imino group (preferably having 2 to 20 carbon atoms, such as phthalimino), acyloxy group (preferably having 1 to 20 carbon atoms) For example, acetyloxy, benzoyl Oxy) or an alkoxycarbonyl group (preferably having a carbon number of 2 to 20, for example, methoxycarbonyl, phenoxycarbonyl), more preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a carboxyl group (including salts thereof) ), A sulfo group (including a salt thereof), an alkoxy group, a carbamoyl group, or an alkoxycarbonyl group.
[0034]
One preferable form of the compound represented by the general formula (1) is represented by the general formula (3). In the general formula (3), R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl, n -Propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2- Chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl) or a halogen atom.
R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , and R ³⁶ are more preferably a hydrogen atom or an alkyl group.
Some of R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ may be bonded to each other to form a ring, and in the case of forming a ring, a cyclohexene ring, a cyclopentene ring, benzene A ring is preferable, but R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , and R ³⁶ are all preferably hydrogen atoms.
[0035]
In the general formula (3), ^{m 3} and ^{n 3} each independently represents an integer of 0 to 4, preferably an integer of 1-3. When m ³ and n ³ are 2 or more, a plurality of R ³² , R ³³ , R ³⁵ and R ³⁶ may be the same or different.
[0036]
In the general formula (3), R ³⁷ represents a hydrogen atom, an alkyl group, or an aryl group.
i ³ represents an integer of 0 to 4, preferably an integer of 0 to 2, and most preferably 0. When i ³ is 1 or more, the plurality of R ³⁷ may be the same or different.
[0037]
In the general formula (3), X ³¹ and X ³² represent a group represented by the following general formula (4), and may be the same or different.
General formula (4)
[0038]
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[0039]
In the general formula (4), R ³⁸ represents a hydroxy group, an alkoxy group (preferably having a carbon number of 1 to 16, such as methoxy, ethoxy, butoxy, cyclohexyloxy), an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino. Represents a group. R ⁴⁰ and R ⁴¹ are each independently a hydrogen atom, a hydroxy group, an alkoxy group (preferably having a carbon number of 1 to 16, such as methoxy, ethoxy, butoxy, cyclohexyloxy), an alkylamino group, a dialkylamino group, an arylamino group, Or represents a diarylamino group. ^R38 is preferably a dialkylamino group or a diarylamino group. R ⁴⁰ and R ⁴¹ are each preferably a hydrogen atom.
[0040]
In the general formula (4), R ³⁹ is an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl. , Carboxymethyl, 5-carboxypentyl).
[0041]
One preferable form of the compound represented by the general formula (2) is represented by the general formula (5). In the general formula (5), R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n -Butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, 2-chlorophenyl, 4-methoxyphenyl) , 3-methylphenyl, 1-naphthyl) or a halogen atom.
R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are more preferably a hydrogen atom or an alkyl group.
Some of R ⁵¹ , R ⁵² , R ⁵³ , and R ⁵⁴ may be bonded to each other to form a ring, but R ⁵¹ , R ⁵² , R ⁵³ , and R ⁵⁴ may all be hydrogen atoms. preferable.
[0042]
In the general formula (5), ^{m 5} and ^{n 5} each independently represents an integer of 1 to 4, preferably an integer of 1-3. When m ⁵ and n ⁵ are 2 or more, a plurality of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different.
[0043]
In the general formula (5), R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group or an aryl group (preferred examples are the same as R ^{51 to} R ⁵⁴ ), preferably an alkyl group, more preferably none. It represents a substituted alkyl group, or an alkyl group substituted with a sulfo group or a carboxyl group, and more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms or a sulfoalkyl group having 1 to 4 carbon atoms.
[0044]
In the general formula (5), Z ⁵¹ and Z ⁵² each independently represent an atomic group forming a 5- or 6-membered ring. The heterocycle formed is preferably an indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, benzoxazole ring, oxazole ring, oxazoline ring, benzimidazole ring, imidazole ring, thiadiazole ring Quinoline ring, pyridine ring, more preferably indolenine ring, azaindolenine ring, pyrazoline ring, benzothiazole ring, thiazole ring, thiazoline ring, thiadiazole ring, quinoline ring, particularly preferably indolenine ring, It is an azaindolenine ring.
[0045]
In the general formula (5), the heterocycle formed by Z ⁵¹ and Z ⁵² may have a substituent, and the substituent is preferably an alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, ethyl , N-propyl, isopropyl, n-butyl, n-pentyl, benzyl, 3-sulfopropyl, 4-sulfobutyl, carboxymethyl, 5-carboxypentyl), an alkenyl group (preferably having 2 to 20 carbon atoms such as vinyl, Allyl), a cycloalkyl group (preferably having 3 to 20 carbon atoms, such as cyclopentyl, cyclohexyl), an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, 2-chlorophenyl, 4-methoxyphenyl, 3-methylphenyl, 1-naphthyl), a heterocyclic group (preferably having 1 to 20 carbon atoms, for example, pyridyl, thienyl Furyl, thiazolyl, imidazolyl, pyrazolyl, pyrrolidino, piperidino, morpholino), alkynyl group (preferably having 2 to 20 carbon atoms, for example, ethynyl, 2-methylethynyl, 2-phenylethynyl), halogen atom (for example, F, Cl, Br, I), an amino group (preferably having 1 to 20 carbon atoms, for example, dimethylamino, diethylamino, dibutylamino), cyano group, hydroxyl group, carboxyl group, sulfo group, acyl group (preferably having 1 to 20 carbon atoms, For example, acetyl, benzoyl, salicyloyl, pivaloyl), an alkoxy group (preferably having 1 to 20 carbon atoms, such as methoxy, butoxy, cyclohexyloxy), an aryloxy group (preferably having 6 to 26 carbon atoms, such as phenoxy, 1- Naphthoxy), alkylthio group (preferably Or an arylthio group (preferably 6-20 carbons such as phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (preferably 1-20 carbons such as, for example, Methanesulfonyl, butanesulfonyl), arylsulfonyl groups (preferably having 6 to 20 carbon atoms, such as benzenesulfonyl, paratoluenesulfonyl), carbamoyl groups (preferably having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl), acylamino group (preferably having 1 to 20 carbon atoms, such as acetylamino, benzoylamino), imino group (preferably having 2 to 20 carbon atoms, such as phthalimino), acyloxy group (preferably having 1 to 20 carbon atoms) For example, acetyloxy, benzoyl Oxy) or an alkoxycarbonyl group (preferably having a carbon number of 2 to 20, for example, methoxycarbonyl, phenoxycarbonyl), more preferably an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a carboxyl group (including salts thereof) ), A sulfo group (including a salt thereof), an alkoxy group, a carbamoyl group, or an alkoxycarbonyl group, and more preferably an alkyl group, an aryl group, a carboxyl group (including a salt thereof), a sulfo group (including a salt thereof). Or a carbamoyl group.
[0046]
Hereinafter, preferred specific examples of the two-photon absorption material and the non-resonant two-photon light emitting material represented by the general formula (1) or (2) used in the present invention will be given, but the present invention is not limited to these. is not.
[0047]
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[0048]
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[0049]
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[0050]
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[0051]
Examples of the use of the non-resonant two-photon absorption material and the non-resonant two-photon light-emitting material of the present invention include the above-mentioned Patent Document 1, Bahawalkar, J. et al. D. et al. Rep. Prog. Phys. 1996, 59, page 1041, as shown in infrared detection method, infrared laser light intensity distribution detection method, glasses for protecting eyes from infrared light, infrared light converted into visible light Wavelength converter, optical limiting, singlet oxygen generation method, cell imaging, PDT, up-conversion laser, microfabrication, and three-dimensional optical recording medium. The non-resonant two-photon absorption material and the non-resonant two-photon light-emitting material of the present invention are particularly effective for cell imaging, PDT, optical limiting, microfabrication, and three-dimensional optical recording media.
[0052]
【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.
[0053]
[Example 1]
[Synthesis of A-1]
[0054]
Compound A-1 of the present invention can be synthesized by the following method.
Further, other compounds of the present invention can be synthesized in the same manner as the synthesis method of A-1 by changing the raw materials used in the reaction.
However, the synthesis method of the compound of the present invention is not limited to this.
[0055]
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[0056]
The starting compound 4-cyclohepten-1-one (1) was obtained from Donald J. et al. It was synthesized by the method described by Marquardt et al., Synthetic Communications, Vol. 18, 1193, 1988.
[0057]
6.6 g (60 mmol) of 4-cyclohepten-1-one (1) was dissolved in 50 ml of dichloromethane, and 1.5 g of CaCO ₃ was added with stirring under a nitrogen atmosphere at −70 ° C., followed by 10 g of Br ₂ (62 .6 mmol) was slowly added dropwise. After stirring for 1 hour, the temperature was raised to room temperature, and stirring was continued for another 40 minutes. Sodium bicarbonate water was added to the reaction solution, and the mixture was extracted with dichloromethane. The organic layer was dried over MgSO ₄ , and then the solid obtained by concentrating the organic layer was recrystallized from cyclohexane to give 4,5-dibromocyclohexanone (2 ) Of 9.1 g (yield: 56%) was obtained.
[0058]
6.5 g (37 mmol) of 4,5-dibromocyclohexanone (2) and 5.0 g (18.5 mmol) of N, N-dimethylaminocinnamaldehyde were dissolved in 100 ml of methanolic HCl, and the mixture was stirred at 70 ° C. for 5 hours under a nitrogen atmosphere. Stir. Sodium bicarbonate water was added to the reaction solution, extracted with dichloromethane, and the organic layer was dried over MgSO ₄ and concentrated to obtain red crystals. The obtained crude crystals were suspended in ethyl acetate, refluxed for about 15 minutes, and then filtered to obtain 6.5 g (yield: 60%) of orange crystals of compound 3.
[0059]
0.9 g (1.54 mmol) of Compound 3 was suspended in dehydrated THF (100 ml) and 1,8-diazabicyclo [5,4,0] -7-undecene (DBU) 0 while stirring at room temperature under a nitrogen atmosphere. .47 g (3.1 mmol) was added dropwise and stirred for 1 hour. Further, 1.0 g (6.6 mmol) of DBU was added and stirred for 1 hour, and then 1.0 g (6.6 mmol) of DBU was added again. After this operation was repeated twice, the reaction solution was stirred for 1 hour while warming to 40 ° C., allowed to cool and the precipitated brown solid was filtered off, and the obtained filtrate was extracted with brine / dichloromethane. The organic layer was dried over MgSO ₄ and concentrated to obtain black crude crystals. The obtained crude crystals were purified by silica gel column chromatography (developing solvent; chloroform: hexane = 3: 1) to obtain 0.41 g (yield: 62%) of dark purple crystals of the compound A-1 of the present invention. .
¹ H NMR spectrum (solvent: Chloroform-d ³ ): 3.02 (s, 12H), 6.07 (d, 2H), 6.67 (d, 4H), 6.71 (d, 2H), 6 .96 (d, 2H), 7.14 (t, 2H), 7.42 (d, 4H), 7.51 (d, 2H)
[0060]
[Example 2]
[Method for evaluating two-photon absorption cross section]
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. This measurement method is a method for comparing the intensity of light emission from an excited state induced by non-resonant two-photon absorption between a reference substance and a substance to be measured, and must be a compound that causes two-photon emission. Although it cannot be measured, it is characterized in that a simpler and relatively accurate value can be obtained as compared with other methods. 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, 13, 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 in chloroform at a concentration of 1 × 10 ⁻³ was used.
[0061]
The two-photon absorption cross section of the compound A-1 of the present invention was measured by the above method, and the obtained results were shown below in GM units (1GM = 1 × 10 ⁻⁵⁰ cm ⁴ s / photon). In addition, the value shown below is the maximum value of the two-photon absorption cross section within the measurement wavelength range. The two-photon absorption cross sections of the following comparative compounds measured in the same manner except that benzyl alcohol was used as a solvent are also shown.
[0062]
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[0063]
As indicated above, the present invention has yielded good non-resonant two-photon absorption / emission characteristics that far exceed conventional materials.
[0064]
【The invention's effect】
By using the compound of the present invention, it is possible to provide a material that performs non-resonant two-photon absorption and emission much more efficiently than before.

Claims (5)

A non-resonant two-photon absorption material comprising a compound represented by the following general formula (1) or the following general formula (2).
General formula (1)

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ each independently represents a hydrogen atom or a substituent, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ Some of them may combine with each other to form a ring. m and n each independently represents an integer of 0 to 4, and when m ¹ and n ¹ are 2 or more, a plurality of R ¹² , R ¹³ , R ¹⁵ and R ¹⁶ may be the same or different. R ¹⁷ represents a substituent, and i ¹ represents an integer of 0 or more and 4 or less. When i ¹ is 2 or more, the plurality of R ¹⁷ may be the same or different. X ¹¹ and X ¹² represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and may be the same or different.
General formula (2)

In the formula, R ²¹ , R ²² , R ²³ , and R ²⁴ each independently represent a hydrogen atom or a substituent, and some of R ²¹ , R ²² , R ²³ , and R ²⁴ are bonded to each other to form a ring. May be formed. m ² and n ² each independently represent an integer of 1 to 4, and when m ² and n ² are 2 or more, a plurality of R ²¹ , R ²² , R ²³ and R ²⁴ may be the same or different. . R ²⁵ represents a substituent, and i ² represents an integer of 0 or more and 4 or less. If i ² is 2 or more, plural R ²⁵ may be the same or different. R ²⁶ and R ²⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ²¹ and Z ²² are each independently required to form a nitrogen-containing 5- or 6-membered ring. Represents an atomic group. A nonresonant two-photon light emitting material comprising the compound represented by the general formula (1) or the general formula (2) according to claim 1. A non-resonant two-photon absorption material containing the compound represented by the general formula (1) or the general formula (2) according to claim 1 is irradiated with laser light having a wavelength longer than a linear absorption band of the compound. A non-resonant two-photon absorption inducing method characterized by inducing two-photon absorption. A non-resonant two-photon light-emitting material containing the compound represented by the general formula (1) or the general formula (2) according to claim 2 is irradiated with laser light having a wavelength longer than the linear absorption band of the compound. A method for generating non-resonant two-photon emission, which induces non-resonant two-photon absorption and generates light emission. A methine compound represented by the following general formula (3) or the following general formula (5).
General formula (3)

In the formula, R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and R ³¹ , R ³² , R ³³ , R ³⁴ , When R ³⁵ and R ³⁶ are alkyl groups, some of R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ and R ³⁶ may be bonded to each other to form a ring. m ³ and n ³ each independently represents an integer of 0 to 4, and when m ³ and n ³ are 2 or more, a plurality of R ³² , R ³³ , R ³⁵ and R ³⁶ may be the same or different. . R ³⁷ represents a hydrogen atom, an alkyl group, or an aryl group, and i ³ represents an integer of 0 or more and 4 or less. When i ³ is 2 or more, the plurality of R ³⁷ may be the same or different. X ³¹ and X ³² represent a group represented by the following general formula (4), and may be the same or different.
General formula (4)

In the formula, R ³⁸ represents a hydroxy group, an alkoxy group, an alkylamino group, a dialkylamino group, an arylamino group, or a diarylamino group, and R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, a hydroxy group, an alkoxy group, an alkyl An amino group, a dialkylamino group, an arylamino group, or a diarylamino group is represented. R ³⁹ represents an alkyl group.
General formula (5)

In the formula, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and when R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ are an alkyl group, Some of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be bonded to each other to form a ring. m ⁵ and n ⁵ each independently represent an integer of 1 to 4, and when m ⁵ and n ⁵ are 2 or more, a plurality of R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ may be the same or different. . R ⁵⁵ represents a hydrogen atom, an alkyl group, or an aryl group, and i ⁵ represents an integer of 0 or more and 4 or less. When i ⁵ is 1 or more, the plurality of R ⁵⁵ may be the same or different. R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and Z ⁵¹ and Z ⁵² are each independently required to form a nitrogen-containing 5- or 6-membered ring. Represents an atomic group.