项目名称： 具有非线性光学响应的碳硼烷衍生物设计与合成

项目编号： No.21502072

项目类型： 青年科学基金项目

立项/批准年度： 2016

项目学科： 无机化学

项目作者： 王兆进

作者单位： 盐城工学院

项目金额： 22万元

中文摘要： 如今非线性正被广泛地应用于日常生活，发现新的非线性材料也变得重要。过去二十年中，(金属)有机非线性材料是研究的重点。有机类材料非线性系数高、响应速度快、损伤阈值高以及易于剪裁；金属有机类兼有金属-配体电荷转移，能够提升非线性。构建此类分子的方法是利用芳环连接电子给体和受体。然而单一的芳环体系存在着多样性、可调节性不足等限制。本项目中我们将设计碳硼烷非线性分子。碳硼烷是骨架电子离域的碳硼簇，具有芳香性、碳端缺电子性以及硼端给电子性，可成为芳环的替代者。回顾碳硼烷发光分子，主要源自光诱导电子转移，符合非线性要求。我们尝试着基于已知的有机非线性体系，通过碳硼烷碳端连接替换受体，硼端连接替代给体，或者用碳硼同时连接替代芳基构建非线性体系。另外，用钌金属替换B(3)构建金属碳硼烷，可能得到更好的性能。本项目旨在非线性领域对碳硼烷衍生物进行系统深入的研究，开拓碳硼烷和非线性光学材料的新视野。

中文关键词： 非线性光学；碳硼烷衍生物；分子内电荷转移

英文摘要： Nonlinear optics are being widely used in our social life, and for sake of continuation of this thriving perspective, the pursuing of new NLO materials is thus becoming crucial. As remarkable members of NLO motif, the organic or organometallic nonlinear compounds have been the subject of intense investigation in the last two decades. Compared to the inorganic NLO counterparts, they possess higher non-linear coefficient, faster response, higher damage threshold, more facility for modification, and for organometallic ones, additional MLCT (metal to ligand charge transfer) which significantly improves NLO performances. The basic principle for constructing organic NLO molecules is to connect the electron donor and acceptor with ∏ bridge, which is in general based on aryl or aromatic heterocyclic groups. However, the rigid explorations with aryl systems have brought about considerable limitations such as less diversity, less flexibility, for the findings of more advanced materials. In this funding proposal, we present the designing of NLO molecules which are based on ortho-carobrane. 0-Carborane (C2B10H12) is a polyhedral boron-carbon molecular cluster that stabilized by electron-delocalized covalent bonding in the skeletal framework. Several remarkable features within 0-carorane are the three-dimensional cluster aromaticity, the electron deficiency at carbon sites and the electron sufficiency at boron sites, all of which indicating carborane as a possible alternative of aryl. Carborane derivatives as organic emitting examples have been also reviewed, and the predominant emissive behaviors within them are originated from the photo-induced electron transfer, in good agreements with the requirements of non-linear optics. Based on the well-known organic non-linear systems, we are trying to building possible NLO candidates by replacing the traditional acceptor with C-substituted carborane, the donor with B-substituted carborane, or even the ambiguous conjugator with the C,B-cosubstituted carborane. Besides, by the replacement of B(3) with Ru fragment, the organometallic carborane-based NLO derivatives can also be constructed, and due to the reverse in electron nature of carborane cage, these examples may result in even better NLO performances. Though some effort has already be contributed, this proposal aims at extending the scope of carborane derivatives with more systematic investigations and more specialization in NLO applications. With some expected results at hand, we believe this may open new avenue in both chemistry of carborane and NLO.

英文关键词： non-linear optics;carborane derivatives;intramolecular charge transfer