自旋转换和光致变色双功能性配合物的设计合成、结构与性质

The study of inorganic―organic hybrid complexes with magnetic and optical functional properties is a currently important research subject of inorganic chemistry. The study of the design,synthesis and property of complexes with spin transition multifunctionality is a currently hot topic. In this program, the novel complexes with spin transition and photochromic bifunctionality will be designed and synthesized by the self-assembly of the photochromic ligand of azo―conjugated trizolate (tetrazolate etc.) pyridine and transition metal ions containing Fe(II,III),Co(II) etc..Structures,spin transition and photochromic properties for all complexes will be characterized.The isomeric ligand―driven light―induced spin―change effect (LD―LISC) for these complexes under light irradination will be aroused seriously atttention.The affective and cooperative relation to each other between the spin transition and photochromism will be studied.The structures and stability for all isomers will be calculated and analysed by Density Functional Theory. The spin transition at room temperature and the LD―LISC effect for the solid samples of these complexes are hoped to be observed by controlling the design of molecular structures.The relation between structures and properties for all target complexes will be summarized and concluded.The key data for spin transition and photochromic bifunctional properties of these complexes will be first obtained and they will be very important references for the research of molecular based optical―magnetic switching and optical― magnetic message memory etc.. The complexes with larger Stoke Shift fluorescences will be used to the study of cell labeling and imaging.

无机―有机杂化的磁、光功能性配合物的研究是当今无机化学研究的重要课题。其中，具有自旋转换多功能性配合物的设计合成与性质研究是当前研究的热点之一。围绕这个热点课题，本课题选用具有光致异构变化的偶氮多氮唑吡啶类配体和Fe(II,III)、Co(II)等过渡金属离子构筑自旋转换和光致变色双功能性配合物，研究其结构、光致变色和自旋转换等功能性质，重点研究在光辐射微扰下，配体的顺、反异构驱动的光致自旋转换效应(LD-LISC)，探讨自旋转换与光致变色相互间的促进和协调关系，并通过密度泛函理论对配合物各异构体结构和稳定性进行理论研究，期望通过结构调控实现常温下光致自旋转换和在固相中观察到LD―LISC效应，总结、归纳结构―性质关系，实现该类配合物功能材料在关键性能指标上的自主创新,为该类分子基材料在光磁开关和光磁信息存储等领域的应用提供重要参考，并对具有特征荧光的配合物在细胞标记中应用作初步探究。

本课题设计合成了系列偶氮唑衍生类配体（图1, 2），表征了这些配体的吸收光谱、质谱和核磁共振谱和单晶结构（图2），探究了这些配体的光致变色（热致变色）功能性质（图3）。设计合成了30多重这些配体和电子组态为d4-d7排布的过渡金属离子、稀土金属离子构筑目标配合物（附图4），培养了其单晶，表征其单晶结构、荧光、光致变色和磁学等功能性质（图4,5）。探究了这些配合物在光辐射、温度等微扰下的光致变色性质。以及自旋转换配合物在脱水和吸水后的协同作用对配合物自旋转换性质的影响（图4-7）。总结、归纳结构-性质关系，并通过密度泛函理论对配合物各异构体结构和稳定性进行理论计算。实现了光致变色和自旋转换双功能性配合物在合成方法和关键性能指标上的自主创新,为该类分子基功能配合物材料在光磁开关、光磁记忆和信息存储等领域的应用提供重要的参考。并对具有特征荧光的配合物在细胞标记领域的应用作初步探究（图8）。此外还得到了部分配合物纳米晶体（图9）。