JP6311093B2 - Sensor elements for detecting supramolecular complexes, light emitters, and organic compounds - Google Patents
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Description
本発明は、機能性材料の技術分野に属し、特に、複数の分子を複合して構成される超分子複合体（超分子化合物）に関する。 The present invention belongs to the technical field of functional materials, and particularly relates to a supramolecular complex (a supramolecular compound) composed of a plurality of molecules.
蛍光により発光性が得られる発光材料は、主に有機ＥＬ材料等の電子デバイス用部品として広く利用されている。例えば、発光性ビス（アジニル）メテンホウ素錯体化合物を含有する発光層を含むOLEDデバイス（特許文献１参照）、青色発光ルミネッセンス化合物であるホウ素化合物（特許文献２参照）、ピレン化合物とビス（アジニル）アゼン骨格を有するホウ素錯体とを含有する発光素子（特許文献３参照）などがある。 Luminescent materials that can emit light by fluorescence are widely used mainly as components for electronic devices such as organic EL materials. For example, an OLED device including a light emitting layer containing a light emitting bis (azinyl) methene boron complex compound (see Patent Document 1), a boron compound that is a blue light emitting luminescence compound (see Patent Document 2), a pyrene compound and bis (azinyl) There is a light-emitting element containing a boron complex having an azeene skeleton (see Patent Document 3).
近年、このような従来の電子デバイス用の発光材料として、優れた光学特性および電気化学特性をもつπ共役分子を利用できる発光材料の実現が期待されている。π共役分子は、分子内でπ電子が非局在化されることによって、高い吸光度、広い吸収領域、豊富な波長選択性という優れた特性を有する。このπ共役分子を利用する発光については、例えば、ナフタレンジイミドと芳香族分子(トルエンなど)が、溶媒中で相互作用し、励起錯体発光(エキサイプレックス)を観測することが示されている（非特許文献１）。しかし、この発光は固体中ではなく溶液中での発光であり、さらには絶対発光量子収率は１％以下という低いものである。 In recent years, it has been expected that a light-emitting material that can use a π-conjugated molecule having excellent optical characteristics and electrochemical characteristics as a light-emitting material for such a conventional electronic device. The π-conjugated molecule has excellent properties such as high absorbance, wide absorption region, and abundant wavelength selectivity by delocalizing π electrons in the molecule. With regard to light emission using this π-conjugated molecule, for example, it has been shown that naphthalene diimide and aromatic molecules (toluene, etc.) interact in a solvent and observe exciplex emission (exciplex) (non-native). Patent Document 1). However, this luminescence is luminescence in a solution, not in a solid, and the absolute luminescence quantum yield is as low as 1% or less.
上記の溶液中での発光とは異なり、π共役分子の特性を活かして、充分な発光強度を得るために、複数の分子から構成される固体の超分子複合体も開示されている。例えば、多孔性金属錯体を用いて、ナフタレンジイミドと芳香族分子（トルエン、ベンゼン、キシレンなど）を結晶中で相互作用させることで、励起錯体発光（エキサイプレックス）を示す固体発光材料がある（非特許文献２〜４）。
Unlike the light emission in the solution described above, a solid supramolecular complex composed of a plurality of molecules is also disclosed in order to obtain sufficient light emission intensity by utilizing the characteristics of the π-conjugated molecule. For example, there is a solid light-emitting material that exhibits exciplex emission (exciplex) by interacting naphthalene diimide and aromatic molecules (toluene, benzene, xylene, etc.) in a crystal using a porous metal complex (non-excited)
しかし、該固体発光材料における絶対発光量子収率は、最大で22%という低い値にとどまっている。このように、π共役分子は、特に固体中ではその優れた特性を十分に発揮できないことが知られている。 However, the absolute light emission quantum yield in the solid light-emitting material remains as low as 22% at the maximum. Thus, it is known that a π-conjugated molecule cannot sufficiently exhibit its excellent characteristics particularly in a solid.
さらに、該固体発光材料では、次のような理由により、実用上、多くの問題がある。まず、重金属を用いることから、取り扱いが容易ではなく環境負荷も大きい。さらには、該固体発光材料を得る為に、硝酸亜鉛、テレフタル酸、ナフタレンジイミドをジメチルホルムアミドに溶解させ、95℃ で３日間にわたって反応させることで結晶を取得すること、溶媒分子（ジメチルホルムアミド）を取り除くこと、および、ゲスト分子（トルエン、ベンゼン、キシレンなど）を取り込ませること、という煩雑な複数の工程を経る必要がある。 Further, the solid light emitting material has many problems in practical use for the following reasons. First, since heavy metals are used, handling is not easy and the environmental load is large. Furthermore, in order to obtain the solid light-emitting material, zinc nitrate, terephthalic acid and naphthalenediimide are dissolved in dimethylformamide and reacted at 95 ° C. for 3 days to obtain crystals, and solvent molecules (dimethylformamide) are obtained. It is necessary to go through a plurality of complicated steps of removing and incorporating guest molecules (toluene, benzene, xylene, etc.).
本発明の目的は、上記課題を解決すべく、重金属を用いることなく、さらには簡便な操作によって、複数の構成成分から形成される優れた発光特性を有する超分子複合体を提供することにある。 In order to solve the above problems, an object of the present invention is to provide a supramolecular complex having excellent luminescent properties, which is formed from a plurality of components without using a heavy metal and by a simple operation. .
本発明者らは、窒素原子(N)間とホウ素原子(B)間に働く強い分子間相互作用による配位結合（窒素-ホウ素結合:N-B 結合）に着目したところ、該分子相互作用を活用することによって、固体状態で優れた発光特性を発揮する超分子複合体（包接結晶ともいう）を見出した。また、該超分子複合体は、従来のような重金属を必要としないことのみならず、上記の複数成分を、単に混合するのみという極めて簡便な手法で得られることも見出した。 The inventors focused on the coordination bond (nitrogen-boron bond: NB bond) due to strong intermolecular interaction between nitrogen atoms (N) and boron atoms (B). As a result, a supramolecular complex (also referred to as an inclusion crystal) that exhibits excellent light emission characteristics in a solid state was found. It has also been found that the supramolecular complex does not require a heavy metal as in the prior art, but can be obtained by a very simple method of simply mixing the above-mentioned plurality of components.
かくして、本発明では、芳香族ジイミド化合物または芳香族イミド化合物からなるルイス塩基（ホスト分子；電子受容体）と、３級ホウ素化合物からなるルイス酸と、置換されていてもよいベンゼン、ナフタレン、アントラセン、またはピレンからなる溶媒分子（ゲスト分子；電子供与体）とから構成され、該ルイス塩基に含まれる窒素原子と該ルイス酸に含まれるホウ素原子とが配位結合して構成されていることを特徴とする超分子複合体が提供される。 Thus, in the present invention, a Lewis base (host molecule; electron acceptor) composed of an aromatic diimide compound or an aromatic imide compound, a Lewis acid composed of a tertiary boron compound, and optionally substituted benzene, naphthalene, anthracene. Or a solvent molecule composed of pyrene (guest molecule; electron donor), and a nitrogen atom contained in the Lewis base and a boron atom contained in the Lewis acid are coordinated. A featured supramolecular complex is provided.
（ルイス塩基）
本発明の超分子複合体を構成するルイス塩基を構成する芳香族ジイミド化合物または芳香族イミド化合物は、各々、下記の一般式（Ｉ−１）または一般式（Ｉ−２）で表すことができる。(Lewis base)
The aromatic diimide compound or the aromatic imide compound constituting the Lewis base constituting the supramolecular complex of the present invention can be represented by the following general formula (I-1) or general formula (I-2), respectively. .
上記式中、環Ａは、置換基を有してもよい炭素数６〜２０の芳香族炭化水素環を表し、単環でも複環でもよく、Ｒ１およびＲ２は、互いに独立して、炭素数１〜１０のアルキル鎖で連結されていてもよい、置換もしくは非置換の、ピリジル基、ピリミジル基、ピラジル基、ピリダジル基、トリアジル基、ピロール基、イミダゾール基、ピラゾール基、イソチアゾール基、イソオキサゾール基、フラザン基、チアジアゾール基、トリアゾール基、テトラゾール基、インドール基、もしくはベンゾニトリル基；炭素数１〜１０の直鎖状もしくは分岐鎖状のアルキル基もしくはフルオロ基で置換されていてもよい、アニリン基、もしくはアミノ基；ニトリル基を表す。In the above formula, ring A represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent, and may be monocyclic or polycyclic, and R 1 and R 2 are independently of each other, A substituted or unsubstituted pyridyl group, pyrimidyl group, pyrazyl group, pyridazyl group, triazyl group, pyrrole group, imidazole group, pyrazole group, isothiazole group, which may be linked by an alkyl chain having 1 to 10 carbon atoms, Isoxazole group, furazane group, thiadiazole group, triazole group, tetrazole group, indole group, or benzonitrile group; may be substituted with a linear or branched alkyl group or fluoro group having 1 to 10 carbon atoms Represents an aniline group or an amino group; a nitrile group.
環Ａとしては、１〜４員環の芳香族炭化水素環が好ましく、例えば、ベンゼン環、ナフタレン環、ペリレン環を用いることができる。すなわち、ルイス塩基の例としては、以下の式（ａ−１）〜（ａ−６）で表される化合物を挙げることができるが、溶媒分子を取込みやすい点から、式（ａ−１）〜（ａ−３）で表されるような、嵩高いジイミド化合物を用いることが、より好ましい。 As the ring A, a 1- to 4-membered aromatic hydrocarbon ring is preferable, and for example, a benzene ring, a naphthalene ring, and a perylene ring can be used. That is, examples of the Lewis base include the compounds represented by the following formulas (a-1) to (a-6). From the viewpoint of easy incorporation of solvent molecules, the formulas (a-1) to (a-1) It is more preferable to use a bulky diimide compound represented by (a-3).
上記化合物に含まれるＲ１およびＲ２は、上記で既に記載したものと同一である。なお、このＲ１およびＲ２の例としては、以下の式（ｂ−１）〜（ｂ−２５）で表される置換基を挙げることができるが、取扱いの容易さから、以下の式（ｂ−１）〜（ｂ−６）で表される、ピリジル基またはピリミジル基であることが好ましい。より好ましくは、以下の式（ｂ−１）〜（ｂ−３）で表される、ピリジル基である。R 1 and R 2 contained in the compound are the same as those already described above. Examples of R 1 and R 2 include substituents represented by the following formulas (b-1) to (b-25). For ease of handling, the following formula ( It is preferably a pyridyl group or a pyrimidyl group represented by b-1) to (b-6). More preferably, it is a pyridyl group represented by the following formulas (b-1) to (b-3).
以上の点から、本願発明に用いられるルイス塩基としては、ピリジル基またはピリミジル基で置換された、ピロメリット酸ジイミド化合物、ナフタレンジイミド化合物、またはペリレンジイミド化合物（それぞれ、前記式（ａ−１）、（ａ−２）、または（ａ−３）で表される化合物であって、各式中のＲ１およびＲ２の双方が、ピリジル基またはピリミジル基であるもの）であることが好ましい。
さらに、取扱いの容易さから、以下の式（ｃ−１）〜（ｃ−３）で表されるような、ピリジル基で置換されたナフタレンジイミド化合物、または、以下の式（ｃ−４）〜（ｃ−６）で表されるような、ピリジル基で置換されたピロメリット酸ジイミド化合物であることが、より好ましい。From the above points, as the Lewis base used in the present invention, a pyromellitic acid diimide compound, a naphthalenediimide compound, or a perylene diimide compound substituted with a pyridyl group or a pyrimidyl group (respectively, the formula (a-1), A compound represented by (a-2) or (a-3), wherein both R 1 and R 2 in each formula are a pyridyl group or a pyrimidyl group).
Furthermore, from the ease of handling, naphthalene diimide compounds substituted with a pyridyl group as represented by the following formulas (c-1) to (c-3), or the following formulas (c-4) to A pyromellitic acid diimide compound substituted with a pyridyl group as represented by (c-6) is more preferable.
（ルイス酸）
本発明の超分子複合体を構成するルイス酸を構成する３級ホウ素化合物は、下記の一般式（ＩＩ−１）または一般式（ＩＩ−２）で表すことができる。(Lewis acid)
The tertiary boron compound constituting the Lewis acid constituting the supramolecular complex of the present invention can be represented by the following general formula (II-1) or general formula (II-2).
上記式中、Ｒ３は、フッ素原子、塩素原子、臭素原子、イソプロピル基を含む炭素数３〜１０からなるアルキル基またはフェニル基、ペンタフルオロフェニル基を含むアリール基を表し、Ｒ４は、イソプロピル基または、フェニル基、ペンタフルオロフェニル基を含むアリール基を表す。In the above formula, R 3 represents a fluorine atom, a chlorine atom, a bromine atom, an alkyl group having 3 to 10 carbon atoms including an isopropyl group, or an aryl group including a phenyl group and a pentafluorophenyl group, and R 4 represents isopropyl Group or an aryl group including a phenyl group and a pentafluorophenyl group.
すなわち、このようなルイス酸の例としては、以下の式（ｄ−１）〜（ｄ−８）で表される化合物を挙げることができるが、このうち、取扱いの容易さから、以下の式（ｄ−１）〜（ｄ−６）で表されるような、上記一般式（ＩＩ−１）に該当する３級ホウ素化合物からなることが好ましい。このうち、嵩高い分子であることが好ましいことから、上記のＲ３は、フッ素原子で置換されていてもよいフェニル基であることが好ましく、例えば、以下の式（ｄ−５）で表されるようなトリフェニルボラン、または以下の式（ｄ−６）で表されるようなトリス(ペンタフルオロフェニルボラン) (TPFB)が好ましく、特に好ましくは、より嵩高い分子であるトリス(ペンタフルオロフェニルボラン) (TPFB)である。That is, examples of such Lewis acids include compounds represented by the following formulas (d-1) to (d-8). Among these, for ease of handling, the following formulas It is preferably made of a tertiary boron compound corresponding to the general formula (II-1) as represented by (d-1) to (d-6). Among these, since it is preferable that it is a bulky molecule, the above R 3 is preferably a phenyl group which may be substituted with a fluorine atom, and is represented by, for example, the following formula (d-5). Or tris (pentafluorophenylborane) (TPFB) represented by the following formula (d-6) is preferable, and tris (pentafluorophenyl) which is a more bulky molecule is particularly preferable. Boran) (TPFB).
（溶媒分子）
本発明の超分子複合体を構成する溶媒分子としては、置換されていてもよいベンゼン、ナフタレン、アントラセン、およびピレンが挙げられる。このうち、前記ルイス酸およびルイス塩基の間隙に入り込みやすく、超分子複合体を形成し易いという点から、単環のものが好ましく、例えば、ベンゼン、トルエン、キシレン、フルオロトルエン、１，３，５−トリメチルベンゼン、１，２，４−トリメチルベンゼン、アニソール、メチルアニソール、ヨードベンゼン、フルオロベンゼン、およびジフルオロベンゼンを挙げることができる。(Solvent molecule)
Examples of the solvent molecule constituting the supramolecular complex of the present invention include optionally substituted benzene, naphthalene, anthracene, and pyrene. Of these, monocyclic ones are preferred from the viewpoint of easily entering the gap between the Lewis acid and the Lewis base and forming a supramolecular complex. For example, benzene, toluene, xylene, fluorotoluene, 1, 3, 5 Mention may be made of trimethylbenzene, 1,2,4-trimethylbenzene, anisole, methylanisole, iodobenzene, fluorobenzene and difluorobenzene.
このように、本発明に係る超分子複合体は、上記のルイス塩基（ホスト分子）、ルイス酸、溶媒分子（ゲスト分子）の複数成分により構成されるものであり、従来とは異なり重金属を不要とするものである。さらにこれらの複数成分を単に混ぜるだけで調製することができるという優れた性質を有する。すなわち、本発明に係る超分子複合体は、溶媒分子（ゲスト分子）の種類を変えるだけで、各種の発光波長の異なる、収率および発光時間の優れたものも含む、各種の発光波長を有する、発光体として有用な化合物である超分子複合体である。 Thus, the supramolecular complex according to the present invention is composed of a plurality of components of the above Lewis base (host molecule), Lewis acid, and solvent molecule (guest molecule), and unlike the conventional case, no heavy metal is required. It is what. Furthermore, it has the outstanding property that it can prepare by only mixing these multiple components. That is, the supramolecular complex according to the present invention has various emission wavelengths including those having different emission wavelengths, excellent yield and emission time, by simply changing the kind of solvent molecules (guest molecules). A supramolecular complex which is a compound useful as a light emitter.
その調製例としては、構成成分であるルイス塩基（ホスト分子）、ルイス酸、および溶媒分子（ゲスト分子）を混合し、溶媒分子（ゲスト分子）が煮沸する、もしくは１００℃まで加熱した後、室温で数分間静置することによって、本発明に係る超分子複合体を粉末状で得ることができる。 As a preparation example, the constituent Lewis base (host molecule), Lewis acid, and solvent molecule (guest molecule) are mixed, and the solvent molecule (guest molecule) is boiled or heated to 100 ° C. The supramolecular complex according to the present invention can be obtained in a powder form by allowing to stand for several minutes.
このようにして得られた本発明に係る超分子複合体（包接結晶）は、これら３つの構成成分、すなわち、ルイス塩基（ホスト分子）、ルイス酸、および溶媒分子（ゲスト分子）の組み合わせによって、様々な異なる発光特性を呈する（後述の実施例参照）。さらに、このような発光特性について、本発明に係る超分子複合体（包接結晶）の大部分は、従来よりも高い絶対発光量子収率を示した。特に、m-フルオロトルエンを溶媒分子（ゲスト分子）とした包接結晶では、４０％という高値を示した。この数値は、上述した非特許文献２〜４で示された従来の固体発光材料（最大２２％）よりも約２倍の発光特性を示すものである。
The supramolecular complex (inclusion crystal) according to the present invention thus obtained is composed of a combination of these three components, that is, Lewis base (host molecule), Lewis acid, and solvent molecule (guest molecule). Exhibit a variety of different emission characteristics (see Examples below). Furthermore, with respect to such luminescence characteristics, most of the supramolecular complex (inclusion crystal) according to the present invention showed higher absolute luminescence quantum yield than before. In particular, the inclusion crystal using m-fluorotoluene as a solvent molecule (guest molecule) showed a high value of 40%. This numerical value shows a light emission characteristic approximately twice that of the conventional solid light-emitting material (maximum 22%) shown in
また、ルイス塩基（ホスト分子）とルイス酸の種類を固定して、溶媒分子（ゲスト分子）の種類を様々に入れ替えることによって、各々、異なる発色を呈する超分子複合体（包接結晶）が得られる。例えば、ルイス塩基をピリジル基で置換されたナフタレンジイミド（NDI）とし、ルイス酸をトリス（ペンタフルオロフェニル）ボラン(TPFB)とした場合に、芳香族分子を、ベンゼン、トルエン、キシレン、１，３，５−トリメチルベンゼン、アニソール、ヨードベンゼン、およびフルオロベンゼンの各々に入れ替えた場合、得られた異なる超分子複合体（包接結晶）は、紫外光励起（励起波長３３０〜３８０ｎｍ）によって、各々、青色〜赤色の波長領域に含まれる７色（紫、藍、青、緑、黄、橙、赤）の異なる発色を呈することが示されている（後述の実施例参照）。 In addition, by fixing the type of Lewis base (host molecule) and Lewis acid and changing the type of solvent molecule (guest molecule) in various ways, supramolecular complexes (inclusion crystals) with different colors can be obtained. It is done. For example, when the Lewis base is naphthalenediimide (NDI) substituted with a pyridyl group and the Lewis acid is tris (pentafluorophenyl) borane (TPFB), the aromatic molecule is benzene, toluene, xylene, 1, 3 , 5-trimethylbenzene, anisole, iodobenzene, and fluorobenzene, the obtained different supramolecular complexes (inclusion crystals) are blue, respectively, by ultraviolet light excitation (excitation wavelength: 330 to 380 nm). It has been shown to exhibit different colors of seven colors (purple, indigo, blue, green, yellow, orange, red) included in the red wavelength region (see examples described later).
このような優れた発光メカニズムは、未だ詳細には解明されていないが、この３つの構成成分の構造上の組み合わせ、すなわち、超分子複合体（包接結晶）内でルイス塩基（ホスト分子）とルイス酸との分子間に生じている隙間に溶媒分子（ゲスト分子）が密に取り込まれていることと、分子内の窒素およびホウ素の配位結合による強い分子間相互作用の共存によって、超分子複合体（包接結晶）内でルイス塩基（ホスト分子）と溶媒分子（ゲスト分子）による励起錯体発光(エキサイプレックス)が安定的かつ効率的に誘引されやすい状況を形成しているものと推察される。 Although such an excellent light emission mechanism has not yet been elucidated in detail, the structural combination of these three components, that is, the Lewis base (host molecule) in the supramolecular complex (inclusion crystal) Supramolecules due to the close inclusion of solvent molecules (guest molecules) in the gaps between Lewis acids and molecules and the strong intermolecular interaction due to the coordinate bonds of nitrogen and boron in the molecule. It is inferred that exciplex emission (exciplex) by Lewis base (host molecule) and solvent molecule (guest molecule) in the complex (inclusion crystal) is easily attracted stably and efficiently. The
本発明に係る超分子複合体（包接結晶）は、このような優れた特性を活かして、紫外光照射により蛍光を発する照明材料や表示材料として利用することができる。 The supramolecular complex (inclusion crystal) according to the present invention can be used as an illumination material or a display material that emits fluorescence when irradiated with ultraviolet light, utilizing such excellent characteristics.
また、該超分子複合体は、上述した発光材料としての用途に限定されない。すなわち、該超分子複合体は、溶媒分子（ゲスト分子）を加熱または減圧（真空引き）することにより、容易に離脱できるという特異な性質も有している。この性質を用いて、該溶媒分子（ゲスト分子）が離脱して形成された超分子複合体を、各種有機化合物（特に、溶媒分子）の種類を検出するための、検出用センサー素子として利用することもできる。 Further, the supramolecular complex is not limited to the use as the light emitting material described above. That is, the supramolecular complex also has a unique property that it can be easily detached by heating or depressurizing (evacuating) solvent molecules (guest molecules). Using this property, the supramolecular complex formed by separation of the solvent molecules (guest molecules) is used as a sensor element for detection for detecting the type of various organic compounds (particularly solvent molecules). You can also.
この有機化合物検出用のセンサー素子の使用方法は、超分子複合体（包接材料）を調製する前記調製方法と同じく、被検対象の有機化合物を、該センサー素子に単に混ぜ合わせるのみで（その後、煮沸して室温まで冷却してもよい）、溶媒分子（ゲスト分子）の種類に応じた呈色が得られることから、視覚的に容易に該溶媒分子（ゲスト分子）を同定することができる。このように、単に混ぜ合わせるという簡素な操作のみによって、さらに呈色した色を観察するだけで、被検対象の有機化合物を同定できるという極めて簡便な有機化合物検出用のセンサー素子として利用することができる。 The sensor element for detecting the organic compound is used in the same manner as the preparation method for preparing the supramolecular complex (inclusion material) by simply mixing the organic compound to be tested into the sensor element (then It may be boiled and cooled to room temperature), and a color corresponding to the type of solvent molecule (guest molecule) can be obtained, so that the solvent molecule (guest molecule) can be easily identified visually. . In this way, it can be used as an extremely simple sensor element for detecting an organic compound that can identify an organic compound to be examined by simply observing a colored color by a simple operation of simply mixing. it can.
以下に、本発明の特徴をさらに具体的に示すために実施例を記すが、本発明は以下の実施例によって制限されるものではない。
なお、以下の実施例では、次の機器・装置を使用した。
NMR：AVANCE 500 核磁気共鳴装置（（株）ブルカー製）
蛍光スペクトル：F7000形日立蛍光光度計（（株）日立ハイテク）
絶対発光量子収率測定装置：絶対PL量子収率測定装置（(株)浜松ホトニクス）
発光寿命測定：小型蛍光寿命測定装置Quantaurus-Tau C11367-01 （(株)浜松ホトニクス））
蛍光顕微鏡観察：Leica DM2500(ライカ)
単結晶X線構造解析：CCD単結晶自動X線構造回折装置((株)リガク)
熱重量分析(TG)：TG/DTA 7300（SIIナノテクノロジー）
拡散反射電子スペクトル(UV-vis)：V670型紫外可視分光光度計（（株）日本分光製）
赤外吸収スペクトル(IR)：FT-IR 460plus分光光度計（（株）日本分光社製）EXAMPLES Examples will be described below to more specifically illustrate the features of the present invention, but the present invention is not limited to the following examples.
In the following examples, the following devices and apparatuses were used.
NMR:
Fluorescence spectrum: F7000 Hitachi Fluorometer (Hitachi High-Tech)
Absolute luminescence quantum yield measurement device: Absolute PL quantum yield measurement device (Hamamatsu Photonics Co., Ltd.)
Luminescence lifetime measurement: Compact fluorescence lifetime measurement system Quantaurus-Tau C11367-01 (Hamamatsu Photonics))
Fluorescence microscope observation: Leica DM2500 (Leica)
Single crystal X-ray structure analysis: CCD single crystal automatic X-ray structure diffractometer (Rigaku Corporation)
Thermogravimetric analysis (TG): TG / DTA 7300 (SII nanotechnology)
Diffuse reflection electron spectrum (UV-vis): V670 type UV-visible spectrophotometer (manufactured by JASCO Corporation)
Infrared absorption spectrum (IR): FT-IR 460plus spectrophotometer (manufactured by JASCO Corporation)
（実施例１）
原料となるルイス塩基の合成 Example 1
Synthesis of Lewis base as raw material
還流管付き50 mL丸底フラスコに1,4,5,8 ナフタレンテトラカルボン酸二無水和物(2.50g,mmol, 9.32 mmol) 、3-アミノピリジン(1.95g, 20.7 mmol)、ジメチルホルムアミド(DMF)(20mL)を加え、150℃ で6 時間加熱還流を行った。室温まで冷却後、生じた沈殿をろ別し、DMF により再結晶することで黄土色の針状結晶を得た。バキュームオーブン(50℃)で真空下12 時間乾燥させる事で、黄土色の粉末(ナフタレンジイミド: 以下、化合物"1"という)を得た。(3.01g, 7.16mmol 収率: 77 %)。同定は元素分析により行った。Elemental Analysis: Calcd, C=68.57,H=2.88, N=13.33; Found, C=68.16, H=2.88, N=13.30. In a 50 mL round bottom flask with a reflux tube, 1,4,5,8 naphthalenetetracarboxylic dianhydride (2.50 g, mmol, 9.32 mmol), 3-aminopyridine (1.95 g, 20.7 mmol), dimethylformamide (DMF ) (20 mL) was added, and the mixture was heated to reflux at 150 ° C. for 6 hours. After cooling to room temperature, the resulting precipitate was filtered off and recrystallized with DMF to give ocher needle-like crystals. Ocher powder (naphthalenediimide: hereinafter referred to as compound “1”) was obtained by drying in a vacuum oven (50 ° C.) under vacuum for 12 hours. (3.01 g, 7.16 mmol yield: 77%). Identification was performed by elemental analysis. Elemental Analysis: Calcd, C = 68.57, H = 2.88, N = 13.33; Found, C = 68.16, H = 2.88, N = 13.30.
超分子複合体(包接結晶)の調製Preparation of supramolecular complex (inclusion crystal)
前記化合物1(50 mg, mmol, 1 eq.)、トリス(ペンタフルオロフェニルボラン) (TPFB) (125 mg, mmol, 2eq.)、トルエン10mL をサンプル管に加えた。ホットプレートにてトルエンが煮沸するまで加熱後、室温にて数分間静置した。生じた沈殿をろ別することで、粉末として超分子複合体(以下、前記化合物"1"とトルエン（溶媒）から得られた超分子複合体を"1⊃Toluene"と表す)を得た(178 mg)。元素分析の結果、前記化合物"1"：TPFB：トルエン分子＝1：2：2 の組成で構成される包接結晶である事が明らかとなった。その他の芳香族溶媒中(フルオロベンゼン、m-フルオロトルエン、ベンゼン、o-キシレン、m-キシレン、p-キシレン、1,3,5-トリメチルベンゼン、アニソール、m-メチルアニソール、ヨードベンゼン)においても、前記化合物"1"：TPFB：溶媒分子＝1：2：2 の組成比である包接結晶(以下、前記化合物"1"と"溶媒（Solvent）"から得られた超分子複合体を"1⊃Solvent"と表す)が得られた。 Compound 1 (50 mg, mmol, 1 eq.), Tris (pentafluorophenylborane) (TPFB) (125 mg, mmol, 2 eq.) And 10 mL of toluene were added to the sample tube. After heating until toluene was boiled on a hot plate, it was allowed to stand at room temperature for several minutes. The resulting precipitate was filtered to obtain a supramolecular complex as a powder (hereinafter, the supramolecular complex obtained from the compound “1” and toluene (solvent) is represented as “1" Toluene ”) ( 178 mg). As a result of elemental analysis, it was found that the compound was an inclusion crystal having the composition of “1”: TPFB: toluene molecule = 1: 2: 2. Also in other aromatic solvents (fluorobenzene, m-fluorotoluene, benzene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene, anisole, m-methylanisole, iodobenzene) , The compound "1": TPFB: solvent molecule = 1: 2: 2 inclusion ratio (hereinafter referred to as the supramolecular complex obtained from the compound "1" and "solvent") 1⊃ Solvent ”).
図１では、本発明に係る包接結晶の写真と元素分析の結果を示す（分子構造は溶媒分子の種類を示す）。左上欄から右方向で進んで右下欄まで、ベンゼン(1⊃Benzene)、トルエン(1⊃Toluene)、o-キシレン(1⊃o-Xylene)、m-キシレン(1⊃m-Xylene) 、p- キシレン(1⊃p-Xylene) 、135 トリメチルベンゼン(1⊃1,3,5-Trimetylbenzene)、アニソール(1⊃Anisole)、ヨードベンゼン(1⊃Iodobenzene)の結果を示している。 FIG. 1 shows a picture of an inclusion crystal according to the present invention and the results of elemental analysis (molecular structure indicates the type of solvent molecule). Proceeding from the upper left column to the right to the lower right column, benzene (1⊃Benzene), toluene (1⊃Toluene), o-xylene (1⊃o-Xylene), m-xylene (1⊃m-Xylene), p -The results for xylene (1⊃p-Xylene), 135 trimethylbenzene (1⊃1,3,5-Trimetylbenzene), anisole (1⊃Anisole), iodobenzene (1⊃Iodobenzene) are shown.
また、図2に、本発明に係る 包接結晶(1⊃Solvent)の熱重量分析(TG)の結果を示す。いずれの試料においても、溶媒分子(ゲスト分子)の放出による重量変化が観測された。それぞれの溶媒の沸点より少し高い温度での溶媒放出挙動が観測されたことから、包接結晶中においてホスト分子と溶媒分子（ゲスト分子）との間で相互作用（電荷移動相互作用）が働いていることが考えられる。またいずれの試料においても300 度付近を越えると大きな重量の減少が観測されたが、これは骨格（ホスト分子）の分解挙動に由来するものと考えられる。 FIG. 2 shows the results of thermogravimetric analysis (TG) of the clathrate crystal (1⊃ Solvent) according to the present invention. In all samples, a change in weight due to the release of solvent molecules (guest molecules) was observed. Since the solvent release behavior was observed at a temperature slightly higher than the boiling point of each solvent, an interaction (charge transfer interaction) worked between the host molecule and the solvent molecule (guest molecule) in the inclusion crystal. It is possible that In all samples, a large decrease in weight was observed above 300 ° C., which is thought to be due to the decomposition behavior of the skeleton (host molecule).
単結晶X 線構造解析
本発明に係る超分子複合体（包接結晶）（溶媒分子トルエン；1⊃Toluene）に関する単結晶X 線構造解析の結果を図３に示す。
結果として、化合物1 のピリジル基とTPFB とが窒素-ホウ素結合(N-B 結合)を介して超分子複合体を形成し、その間隙を埋めるかのように溶媒分子（トルエン分子）が取り込まれた包接結晶(1⊃Toluene)であった。電子不足なπ 共役分子(1)をアクセプター(A)、電子豊富なπ共役分子(トルエン)をドナー(D)とすると、D-A-D 型の一次元カラムを形成していた。単結晶から推測される構成成分の組成比は、前記化合物"1" : TPFB : トルエン = 1 : 2 : 2 であり、これは元素分析の結果と一致していた。 Single-crystal X-ray structure analysis FIG. 3 shows the results of single-crystal X-ray structure analysis of the supramolecular complex (inclusion crystal) (solvent molecule toluene; 1⊃Toluene) according to the present invention.
As a result, the pyridyl group of
本発明に係る各種の溶媒分子を用いた超分子複合体（包接結晶）に対する粉末X線回折測定の結果を図4に示す。図４では、上から1⊃m-Methylanisole、1⊃135-Trimetylbenzene、1⊃m-Xylene、1⊃Benzene、1⊃Toluene、1⊃Tolueneの結晶構造から推測されるX線回折パターン、である。いずれの試料においても1⊃Tolueneの結晶構造から推測されるX線回折パターンと類似していたことより、溶媒分子(ゲスト分子)の種類に関わらず、同様の結晶構造を有しているものと考えられる。これは超分子複合体（包接結晶）の元素分析が前記化合物"1":TPFB:溶媒分子=1:2:2であることからも強く示唆される。 FIG. 4 shows the results of powder X-ray diffraction measurement for a supramolecular complex (inclusion crystal) using various solvent molecules according to the present invention. FIG. 4 shows X-ray diffraction patterns estimated from the crystal structures of 1⊃m-Methylanisole, 1⊃135-Trimetylbenzene, 1⊃m-Xylene, 1⊃Benzene, 1⊃Toluene, and 1⊃Toluene from the top. Both samples had similar crystal structures regardless of the type of solvent molecules (guest molecules) because they were similar to the X-ray diffraction patterns estimated from the crystal structure of 1⊃ Toluene. Conceivable. This is strongly suggested by elemental analysis of the supramolecular complex (inclusion crystal) that the compound is “1”: TPFB: solvent molecule = 1: 2: 2.
発光特性の評価
蛍光顕微鏡により評価された本発明に係る超分子複合体（包接結晶）の発光特性を、励起波長 = 330-380 nm 発光波長 > 420 nmで確認した。超分子複合体（包接結晶）としては、1⊃Benzene、1⊃Iodobenzene、1⊃Fluorobenzene, 1⊃Toluene, 1⊃m-Xylene, 1⊃p-Xylene,1⊃135-Trimethylbenzene, 1⊃Anisole, 1⊃m-Methylanisole, 1⊃Iodobenzeneを対象とした。 Evaluation of emission characteristics The emission characteristics of the supramolecular complex (inclusion crystal) according to the present invention evaluated by a fluorescence microscope were confirmed at excitation wavelength = 330-380 nm and emission wavelength> 420 nm. Supramolecular complexes (inclusion crystals) include 1⊃Benzene, 1⊃Iodobenzene, 1⊃Fluorobenzene, 1⊃Toluene, 1⊃m-Xylene, 1⊃p-Xylene, 1⊃135-Trimethylbenzene, 1⊃Anisole, 1⊃m-Methylanisole and 1⊃Iodobenzene were targeted.
いずれの試料においても、数μ〜数十μメートルの結晶性固体であった。また紫外光照射下（励起波長=330-380nm）で結晶から発光する様子が観測された。その発光色は、ベンゼン(1⊃Benzene)で青色、メタキシレン(1⊃m-Xylene)で緑色、ヨードベンゼン(1⊃Iodobenzene)で赤色の発光が観測されるように、用いる溶媒分子(ゲスト分子)の種類の違いにより、異なる発光色を示した。 All samples were crystalline solids of several μ to several tens of μm. In addition, it was observed that light was emitted from the crystal under ultraviolet light irradiation (excitation wavelength = 330-380 nm). The emission colors are blue for benzene (1⊃Benzene), green for meta-xylene (1⊃m-Xylene), and red for iodobenzene (1⊃Iodobenzene). ) Showed different emission colors due to the difference in type.
さらに、固体状態における発光スペクトル測定および発光寿命測定を行った。結果を図５（ａ）および以下の表１に示す。 Furthermore, emission spectrum measurement and emission lifetime measurement in a solid state were performed. The results are shown in FIG. 5 (a) and Table 1 below.
（発光スペクトル測定結果の考察）
このように、本発明に係る超分子複合体（包接結晶）は、紫外光励起(370nm)において、溶媒分子を変えることによって、7色発光（紫、藍、青、緑、黄、橙、赤：紫外光励起(370nm)）を示す固体発光体として機能することが明らかとなった。芳香環に対して電子求引基を持つ溶媒分子であれば紫・藍・青色発光を示し、電子供与基を持つ溶媒分子とすると緑・黄・橙色へとより長波長側へとシフトした。これらの挙動は、励起状態におけるホスト分子(前記化合物1)と溶媒分子（ゲスト分子）との電子のやりとりで生ずる励起錯体発光（エキサイプレックス）に由来するものと考えられる。中でもm-フルオロトルエン(1⊃m-Fluorotoluene)、トルエン(1⊃Toluene)、m-キシレン(1⊃m-Xylene)をゲストとした包接結晶では、30%を超える高い絶対発光量子収率を示した。化合物1とTPFBが形成する超分子複合体が形成する間隙にゲスト分子が密に取り込まれる事が、効率の良い励起錯体発光（エキサイプレックス）形成を誘起している事が考えられる。ヨードベンゼンに関しては、赤色発光を示したが、これは重原子効果に伴うリン光による発光によるものと考えられる。(Consideration of emission spectrum measurement results)
In this way, the supramolecular complex (inclusion crystal) according to the present invention emits seven colors (purple, indigo, blue, green, yellow, orange, red) by changing solvent molecules under ultraviolet light excitation (370 nm). : It became clear that it functions as a solid state light emitter exhibiting ultraviolet light excitation (370 nm). Solvent molecules having an electron withdrawing group for the aromatic ring exhibited violet, indigo and blue emission, while solvent molecules having an electron donating group shifted to longer wavelengths, green, yellow and orange. These behaviors are considered to originate from exciplex emission (exciplex) generated by the exchange of electrons between the host molecule (the compound 1) and the solvent molecule (guest molecule) in the excited state. In particular, inclusion crystals with m-fluorotoluene (1 ⊃m-Fluorotoluene), toluene (1 ⊃Toluene), and m-xylene (1 ⊃m-Xylene) as guests have high absolute luminescence quantum yields exceeding 30%. Indicated. It is conceivable that the guest molecules are densely taken into the gap formed by the supramolecular complex formed by
（発光寿命測定結果の考察）
寿命の観測波長は、それぞれの最大発光波長で測定した（励起波長 365 nm、室温（25oC））。得られた発光寿命測定結果から、その多くは数ナノ秒から数十ナノ秒を示す発光寿命を示すものであり、ホスト分子（前記化合物1）とゲスト分子（溶媒分子）との相互作用で生じる電荷移動相互作用(チャージ-トランスファー相互作用、C-T相互作用)もしくは励起錯体発光（エキサイプレックス）による蛍光発光であることが考えられる。一方で、ヨードベンゼン、オルトヨードトルエン、メタヨードトルエンをゲスト分子（溶媒分子）として用いた場合は、数十マイクロ秒、数百マイクロ秒の長寿命の発光寿命が観測された。重原子（ヨウ素）を含むことから、包接結晶中における重原子効果によりスピン-軌道相互作用が大きくなり、励起三重項からの発光（リン光）が観測されたものである。結晶中で分子運動が制限されているため、室温でもリン光発光が観測されたものと考えられる。(Consideration of luminescence lifetime measurement results)
The observation wavelength of the lifetime was measured at each maximum emission wavelength (excitation wavelength 365 nm, room temperature (25 o C)). From the obtained luminescence lifetime measurement results, most of them exhibit a luminescence lifetime of several nanoseconds to several tens of nanoseconds, and are generated by the interaction between the host molecule (the compound 1) and the guest molecule (solvent molecule). It can be considered that fluorescence is emitted by charge transfer interaction (charge-transfer interaction, CT interaction) or exciplex emission (exciplex). On the other hand, when iodobenzene, orthoiodotoluene, and metaiodotoluene were used as guest molecules (solvent molecules), long-life luminescence lifetimes of several tens of microseconds and several hundred microseconds were observed. Since it contains a heavy atom (iodine), the spin-orbit interaction increases due to the heavy atom effect in the inclusion crystal, and light emission (phosphorescence) from the excited triplet is observed. It is probable that phosphorescence was observed even at room temperature because molecular motion was limited in the crystal.
有機化合物検出用のセンサーとしての使用例
上記化合物1(50 mg, 0.12 mmol, 1eq.)、トリス（ペンタフルオロフェニル）ボラン（B(C6F5)3 , TPFB, 125 mg, 0.24 mmol, 2 eq.）、トルエン(0.10 mL)をメノウ乳鉢に加え、機械的粉砕・混合を15分行ったところ、淡黄色の粉末が得られた。得られた粉末に、紫外光（365 nm）照射を行ったところ、水色発光が観測された。その他、芳香族分子溶媒として、ベンゼン、オルトキシレン、メタキシレン、パラキシレン、1,3,5-トリメチルベンゼン、1-メチルナフタレンを用いたところ、図５（ｂ）に示すように淡黄色から橙色の粉末が得られた。また得られた粉末に、紫外光（365 nm）照射を行ったところ、芳香族分子溶媒の違いによって、水色、緑色、黄色、橙色発光を示す事が観測された。有機化合物の違いを発光色の違いとしてセンシングすることができた。 Example of use as sensor for organic compound detection Compound 1 (50 mg, 0.12 mmol, 1 eq.), Tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 , TPFB, 125 mg, 0.24 mmol, 2 eq.) and toluene (0.10 mL) were added to an agate mortar, and mechanical pulverization and mixing were performed for 15 minutes. As a result, a pale yellow powder was obtained. When the obtained powder was irradiated with ultraviolet light (365 nm), light blue emission was observed. In addition, benzene, ortho-xylene, meta-xylene, para-xylene, 1,3,5-trimethylbenzene, and 1-methylnaphthalene were used as aromatic molecular solvents. As shown in FIG. Of powder was obtained. Further, when the obtained powder was irradiated with ultraviolet light (365 nm), it was observed that light emission of light blue, green, yellow and orange was caused by the difference in the aromatic molecular solvent. We were able to sense the difference in organic compounds as the difference in emission color.
（実施例２）
出発原料を、実施例１の化合物１に代替して、化合物p-NDIを用いて、製造した。(Example 2)
The starting material was prepared using compound p-NDI instead of
原料となるルイス塩基の合成
（p-NDIの合成と同定） Synthesis of Lewis base as raw material (synthesis and identification of p-NDI)
還流管付き200 mLのナスフラスコに1,4,5,8ナフタレンテトラカルボン酸二無水物( NA)(2.5g, 9.3 mmol)と4-アミノピリジン(21 mmol, 2.0g)を20mLのN,N’-ジメチルホルムアミド(DMF)に溶解させ、150℃で4時間還流を行った。室温まで冷却後、生じた沈殿を濾別し、赤褐色固体を得た。この固体を200mLのナスフラスコに加え40mLのDMFに溶解後再結晶させた。この再結晶操作を2回行い、薄橙色結晶を得た。結晶を真空下27時間130℃で加熱することで結晶中に残存するDMFを除去し、橙色結晶を得た。
p-NDIの同定は1H NMR測定により行った。溶媒として重トリフルオロ酢酸CF3COODを利用した。結果を図６および以下の表に示す。得られた結果から、収量3.2 g、収率83%であることが確認された。
p-NDI was identified by 1 H NMR measurement. Deuterated trifluoroacetic acid CF 3 COOD was used as the solvent. The results are shown in FIG. 6 and the following table. From the obtained results, it was confirmed that the yield was 3.2 g and the yield was 83%.
上記で得られた化合物p-NDI (50 mg, 0.12 mmol, 1eq.)、トリス（ペンタフルオロフェニル）ボラン（B(C6F5)3 , TPFB, 125 mg, 0.24 mmol, 2 eq.）、トルエン(0.10 mL)をメノウ乳鉢に加え、機械的粉砕・混合を15分行ったところ、淡黄色の粉末が得られた。Compound p-NDI obtained above (50 mg, 0.12 mmol, 1 eq.), Tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 , TPFB, 125 mg, 0.24 mmol, 2 eq.), Toluene (0.10 mL) was added to an agate mortar, and mechanical pulverization / mixing was performed for 15 minutes. As a result, a pale yellow powder was obtained.
有機化合物検出用のセンサーとしての使用例
得られた粉末に、紫外光（365 nm）照射を行ったところ、水色発光が観測された。その他、芳香族分子溶媒として、ベンゼン、オルトキシレン、メタキシレン、パラキシレン、1,3,5-トリメチルベンゼン、1-メチルナフタレンを用いたところ、淡黄色から橙色の粉末が得られた。また得られた粉末に、紫外光（365 nm）照射を行ったところ、芳香族分子溶媒の違いによって、水色、緑色、黄色、橙色発光を示す事が観測された。有機化合物の違いを発光色の違いとしてセンシングすることができた。 Example of Use as Sensor for Detecting Organic Compound When the obtained powder was irradiated with ultraviolet light (365 nm), light emission was observed. In addition, when benzene, ortho-xylene, meta-xylene, para-xylene, 1,3,5-trimethylbenzene, and 1-methylnaphthalene were used as aromatic molecular solvents, a pale yellow to orange powder was obtained. Further, when the obtained powder was irradiated with ultraviolet light (365 nm), it was observed that light emission of light blue, green, yellow and orange was caused by the difference in the aromatic molecular solvent. We were able to sense the difference in organic compounds as the difference in emission color.
（実施例３）
出発原料を、実施例１の化合物１に代替して、以下に述べる化合物２を用いて、製造した。(Example 3)
The starting material was prepared using
原料となるルイス塩基の合成
（化合物２の合成と同定） Synthesis of Lewis base as raw material (Synthesis and identification of compound 2)
還流管付き200 mLのナスフラスコにピロメリット酸二無水物 (3.47 g, 15.9 mmol)と3-アミノピリジン(3.0 g, 31.9 mmol)を20 mLのN,N’-ジメチルホルムアミド(DMF)に溶解させ、150℃で6時間還流を行った。室温まで冷却後、生じた沈殿を濾別し、黄色固体を得た。この固体を200 mLのナスフラスコに加え40 mLのDMFに溶解後再結晶させた。この再結晶操作を2回行い、黄色結晶を得た。バキュームオーブンで12時間150℃で加熱することで結晶中に残存するDMFを除去し、黄色の粉末を得た。(4.44g, 12.0mmol収率: 75 %)。同定は元素分析により行った。Elemental Analysis: Calcd, C=64.87, H=2.72, N=15.30; Found, C=64.61, H=2.70, N=15.05. Dissolve pyromellitic dianhydride (3.47 g, 15.9 mmol) and 3-aminopyridine (3.0 g, 31.9 mmol) in 20 mL N, N'-dimethylformamide (DMF) in a 200 mL eggplant flask with a reflux tube The mixture was refluxed at 150 ° C. for 6 hours. After cooling to room temperature, the resulting precipitate was filtered off to obtain a yellow solid. This solid was added to a 200 mL eggplant flask and dissolved in 40 mL of DMF and recrystallized. This recrystallization operation was performed twice to obtain yellow crystals. DMF remaining in the crystals was removed by heating at 150 ° C. for 12 hours in a vacuum oven to obtain a yellow powder. (4.44 g, 12.0 mmol yield: 75%). Identification was performed by elemental analysis. Elemental Analysis: Calcd, C = 64.87, H = 2.72, N = 15.30; Found, C = 64.61, H = 2.70, N = 15.05.
上記で得られた化合物２(50 mg, 0.135mmol, 1 eq.)、トリス(ペンタフルオロフェニルボラン) (TPFB) (140 mg, 2eq.)、オルトキシレン10mL をサンプル管に加えた。ホットプレートにてメタキシレンが煮沸するまで加熱後、室温にて3日間静置した。生じた沈殿をろ別することで、粉末として超分子複合体(以下、前記化合物"2"とオルトキシレン（溶媒）から得られた超分子複合体を"2⊃o-Xylene"という)を得た(197 mg)。その他の芳香族溶媒中(m-キシレン、p-キシレン、1,3,5-トリメチルベンゼン、1,2,4-トリメチルベンゼン、アニソール、ブロモベンゼン、ヨードベンゼン)においても、包接結晶(以下、前記化合物"2"と"溶媒"から得られたものを"2⊃Solvent"という)が得られた。 Compound 2 (50 mg, 0.135 mmol, 1 eq.) Obtained above, tris (pentafluorophenylborane) (TPFB) (140 mg, 2 eq.), And 10 mL of orthoxylene were added to the sample tube. After heating until meta-xylene was boiled on a hot plate, it was allowed to stand at room temperature for 3 days. The resulting precipitate is filtered off to obtain a supramolecular complex as a powder (hereinafter, the supramolecular complex obtained from the compound “2” and ortho-xylene (solvent) is referred to as “2⊃o-Xylene”). (197 mg). In other aromatic solvents (m-xylene, p-xylene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, anisole, bromobenzene, iodobenzene), the inclusion crystal (hereinafter, What was obtained from the compound “2” and “solvent” was referred to as “2⊃ Solvent”.
以下の表および図７に、包接結晶(2⊃Solvent)の発光特性を示した。励起波長は365 nm。ブロモベンゼン、ヨードベンゼンをゲストとした場合の励起波長は340nm、寿命の観測波長はそれぞれの最大発光波長で測定した。室温（25oC）。The following table and FIG. 7 show the emission characteristics of the inclusion crystal (2⊃ Solvent). The excitation wavelength is 365 nm. When bromobenzene and iodobenzene were used as guests, the excitation wavelength was 340 nm, and the lifetime observation wavelength was measured at the respective maximum emission wavelength. Room temperature (25 ° C).
図７の結果から、ゲスト分子の違いにより、青色（466nm）から黄緑色(541nm)の発光を示し、絶対発光量子収率の多くは10%を超える高い値を示した。発光寿命に関しては、キシレン、トリメチルベンゼン、アニソールがゲスト分子の場合にはナノ秒オーダーであったことより、ホスト分子（前記化合物2）とゲスト分子（溶媒分子）との相互作用で生じるチャージトランスファー相互作用(C-T相互作用)もしくは励起錯体発光（エキサイプレックス）による蛍光発光であることが考えられる。一方で、ブロモベンゼン、ヨードベンゼンをゲスト分子（溶媒分子）として用いた場合は、990マイクロ秒、103マイクロ秒の長寿命の発光寿命が観測された。重原子（臭素、ヨウ素）を含むことから、包接結晶中における重原子効果によりスピン-軌道相互作用が大きくなり、励起三重項からの発光（リン光）が観測されたものである。結晶中で分子運動が強く制限されているため、室温でもリン光発光が観測されたものと考えられる。 From the results shown in FIG. 7, the emission from blue (466 nm) to yellow-green (541 nm) was shown depending on the guest molecule, and many of the absolute emission quantum yields were high values exceeding 10%. Regarding the emission lifetime, when xylene, trimethylbenzene, and anisole are guest molecules, they are in the order of nanoseconds, and thus charge transfer mutuals generated by the interaction between the host molecule (the compound 2) and the guest molecule (solvent molecule). It is considered that fluorescence is emitted by action (CT interaction) or exciplex emission (exciplex). On the other hand, when bromobenzene and iodobenzene were used as guest molecules (solvent molecules), long emission lifetimes of 990 microseconds and 103 microseconds were observed. Since it contains heavy atoms (bromine and iodine), the spin-orbit interaction increases due to the heavy atom effect in the inclusion crystal, and light emission (phosphorescence) from the excited triplet is observed. It is probable that phosphorescence was observed even at room temperature because molecular motion was strongly limited in the crystal.
Claims (10)
ルイス酸が、前記一般式（ＩＩ−１）で表される３級ホウ素化合物からなり、Ｒ３が、フッ素原子で置換されていてもよいフェニル基であることを特徴とする請求項１〜請求項３に記載の超分子複合体。 The Lewis base is an aromatic diimide compound represented by the general formula (I-1), and R 1 and R 2 are each independently a pyridyl group or a pyrimidyl group,
Lewis acid consists tertiary boron compound represented by the general formula (II-1), R 3 is, claims 1, characterized in that it is which may be a phenyl group substituted by fluorine atoms Item 4. The supramolecular complex according to Item 3 .
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