无机-有机杂化红外非线性光学材料基础研究

Design and preparation of inorganic-organic hybrid materials for infrared nonlinear optics have already become the research frontier and focus in the fields of materials science and information technology. In this proposal, aiming at the key scientific issues of the controllable construction and functional modification of metal-organic coordination compounds and coordination polymers, the conjugated organic molecules will be designed and synthesized, and then react with the inorganic metal ions to construct the inorganic-organic hybrid materials with infrared nonlinear optical properties. The assembling of coordination compounds and coordination polymers will be systematically investigated, and then the design ideas and synthesis methods of hybrid nonlinear optical materials with expected structure will be established. The functional modification of porous coordination polymer will be developed utilizing the encapsulation of organic chromophore molecules with high nonlinear susceptibility into the pores, then the molecular orientation and arrangement of the chromophores will be investigated. The hybrid effect between organic and inorganic component will be discovered in detail, and the relationship between microstructure and nonlinear optical behavior will be thoroughly investigated and demonstrated. The potential applications of various inorganic-organic hybrid infrared nonlinear optical materials in the fields of frequency conversion, three-dimensional optical storage, ion recognition and biography will be developed. Through the implementation of this proposal, the novel ideas and methods can be obtained for the assembly of inorganic-organic hybrid infrared nonlinear optical materials.

设计制备高性能的无机-有机杂化红外非线性光学材料是材料科学与信息科学的新兴热点和前沿领域。本项目将针对金属有机配合物和配位聚合物这类杂化红外非线性光学材料的定向组装与功能修饰等关键科学问题，设计合成电子共轭程度高的有机配体与特定金属离子或团簇进行组装，构筑新型无机-有机杂化红外非线性光学材料并建立其可控组装方法。选择使用高非线性极化率的有机生色团分子对多孔配位聚合物进行孔道修饰，探明生色团分子在孔道中的取向排列及其发光机制，完善杂化非线性光学材料的功能修饰方法。研究无机-有机杂化材料中有机配体与金属离子或团簇的功能复合效应，建立红外非线性光学性质与微观结构之间的内在联系，实现功能的协同增强与调控优化。选择性能优异的无机-有机杂化红外非线性光学材料，探索在频率转换、三维光存储、离子识别和生物显影等方面的应用。为无机-有机杂化红外非线性光学材料的设计制备及应用提供新思想和新方法。

研究按计划进行，围绕无机-有机杂化红外非线性光学材料的结构设计、可控制备和性能调控等关键问题，设计合成了一系列多孔配位聚合物和金属配合物等新型无机-有机杂化材料，研究建立了杂化材料的可控制备方法。结合理论计算，系统阐明了杂化材料中有机分子的取代基团、桥联基团、同核和多核金属的变化与光物理性质之间的构效关系，揭示了有机分子与金属离子杂化轨道的匹配和能量传递对非线性光学性能的影响机理，研究了杂化材料在超快激光作用下的二/三阶非线性光学和双光子吸收效应，探明了杂化材料在红外波段非线性光学性能增强的微观机制与调控规律。研究了有机生色团分子在配位聚合物孔道中的有序组装过程及其堆积结构、聚集形态与非线性光学性能之间的关联关系，建立了无机-有机杂化非线性光学材料的后功能修饰方法。获得了一批具有超快响应、高损伤阈值的新型红外非线性光学杂化材料，探索了它们在高密度光存储、多光子激射、荧光传感、生物成像、离子识别、生物特异性与诊疗等方面的应用，取得了一系列原创性研究成果。