Development of Non-linear Optical Material involving the Boron Atom

涉及硼原子的非线性光学材料的开发

• 批准号: 06554027
• 负责人: SUGIHARA Yoshikazu
• 金额: $ 3.52万
• 依托单位: Yamaguchi University (1995)Osaka University (1994)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Developmental Scientific Research (B)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06554027/
• 关键词: non-linear optical materials; polarizability; dipole moment; donor and acceptor of pi-electron; conjugated system involving the boron atom; polarized and stable hetero-aromatic molecule; 青色光透過性

To date, conjugated systems, each being composed of a donor, an aromatic ring and an acceptor, have been the well-known non-linear optical materials, in particular, for the purpose of second harmonic generation. We consider that the main role of the aromatic ring are to decrease donation of pi-electron from the donor to the acceptor in the electronically ground state and, accordingly, to relatively enhance the interaction in the electronically excited state. In spite of the marked efficiency of these systems, the recent examinations have stressed that the closed-shell character of the aromatic rings endows the systems with the upper-limit as non-linear optical materials.A trivalent boron is isoelectronic to a carbocation. Hence, it behaves as a pi-electron acceptor. Due to the electropositivity, however, its pi-type conjugation with the carbon atom is considered to be weak like the closed-shell aromatic rings. From this viewpoint we examined borepin annelated with heteroles, such as th … More e pyrrole or thiophene rings both of which are electron donors. After some trials, synthesis of 1-phenylthieno- [3,4-d] borepin (1), 1-phenylthieno [2,3-d] borepin (2), 5-Methyl-1-phenylpyrrolo [3,4-d] borepin (3), and 5-tris (isopropylsilyl)-1-phenylpyrrolo [3,4-d] borepin (4) were achieved. The methods developed are generally useful for the synthesis of conjugated aromatics involving a boron atom. The marked difference in reactivity toward acetic acid was observed with the change of the annelation modes of borepin and heterole rings. The shifts of fluorescent emissions showed the clear linear relationship with the change of solvent-polarity and indicated that the dipole moment of each compound in the excited state is much larger than that in the ground state. The moderate blue-light transparency was observed, despite the above-mentioned charge-transfer character in the excited state.These findings indicate that conjugated systems involving the boron atom are useful as non-linear optical materials. Less

迄今为止，共轭系统是众所周知的非线性光学材料，每个系统由一个施主、一个芳香环和一个受体组成，特别是用于二次谐波的产生。我们认为芳环的主要作用是在电子基态下减少给体对受体的pi电子捐赠，相应地在电子激发态下相对增强相互作用。尽管这些系统的效率显著，但最近的研究强调，芳香环的闭壳特性赋予了系统作为非线性光学材料的上限。三价硼与碳正离子是等电子的。因此，它表现为一个电子受体。然而，由于电正性，它与碳原子的π型共轭被认为像闭壳芳香环一样弱。从这一观点出发，我们研究了与杂杂化合物（如吡咯环或噻吩环）相连的硼甲素，它们都是电子供体。经过一些实验，合成了1-苯基噻吩- [3,4-d] borepin(1)、1-苯基噻吩[2,3-d] borepin(2)、5-甲基-1-苯基吡咯[3,4-d] borepin(3)和5-三（异丙基硅基）-1-苯基吡咯[3,4-d] borepin(4)。所开发的方法一般适用于含硼原子的共轭芳烃的合成。对乙酸的反应性随硼酸素和杂环的合成方式的改变而有显著差异。荧光发射的变化与溶剂极性的变化呈明显的线性关系，表明每种化合物在激发态的偶极矩远大于基态。尽管在激发态具有上述电荷转移特性，但仍观察到适度的蓝光透明。这些发现表明，含硼原子的共轭体系是一种有用的非线性光学材料。少

项目成果

杉原美一: "The Structure of Diethyl (3-pyridyl) borane" J.Chem.Soc.,Chem.Commun.1925-1926 (1994)

Yoshikazu Sugihara：“二乙基（3-吡啶基）硼烷的结构”J.Chem.Soc.，Chem.Commun.1925-1926 (1994)

S.Wakabayashi: "Some Preparation Methods of a Tricyclo [4.1.0.0^<2,7>] -hept-4-en-3-one Skeleton" Synth.Commun.25, No.13. 2019-2027 (1995)

S.Wakabayashi：“三环[4.1.0.0^<2,7>]-hept-4-en-3-one骨架的一些制备方法”Synth.Commun.25，No.13。

Y.Sugihara: "5-Methyl-1-phenylpyrrolo [3,4-d] borepin : A Polarized Aromatic Molecule" J.Chem.Soc., Chem.Commum.No.12. 1249-1250 (1995)

Y.Sugihara：“5-甲基-1-苯基吡咯并[3,4-d]钻硼烷：极化芳香族分子”J.Chem.Soc.，Chem.Commum.No.12。

T.Nakazawa: "The Reactions of 4,5-Dehydrotropone with 4-Phenyloxazols" Tetrahedron Lett.35. 8421-8424 (1994)

T.Nakazawa：“4,5-脱氢托酮与 4-苯基恶唑的反应”Tetrahedron Lett.35。

杉原美一: "Cyclopenta [a] phenalen-9 (8H) -one : An Extended Phenalenone System" J.Chem.Soc.,Perkin Trans.1. 2813-2815 (1995)

Yoshikazu Sugihara：“Cyclopenta [a] phenalen-9 (8H) -one：扩展的 Phenalenone 系统”J.Chem.Soc.，Perkin Trans.1 2813-2815 (1995)。