螺旋结构有机有机金属配合物电子和光物理性质的理论研究-无机化学专业论文.docxVIP

结构；9,9’一位取代对体系的带隙影响很小；螺旋噻吩齐聚物9,9’-位取代对体系的IP和 结构；9,9’一位取代对体系的带隙影响很小；螺旋噻吩齐聚物9,9’-位取代对体系的IP和 EA有一定影响；螺旋交叉双芴噻吩齐聚物较其他三类体系更容易失去电子而形成空穴。 9,9，一位取代对体系的最大吸收位移影响不大，其最低激发跃迁主要是由单链芴基齐噻吩 决定；指出螺旋连接芴基噻吩二聚物的吸收来自于离域激发，两链间没有明显的偶合作 用。 4．采用DFT．B3LYP和从头算组态相互作用方法，以螺旋型有机金属配合物 Zn(PyIm)2为模型，探索激发态几何松弛规律和激发态频率影响的主要因素。系统分析 d”中心金属离子Zn对螺旋结构体系基态与激发态结构变化差异的贡献与作用。同时对 比Bepp2体系，指出影响规律。 关键词：螺旋结构，芴，齐聚噻吩，DFT，ZINDO，定域密度矩阵，带隙，电子光谱 II AbstractOrganic Abstract Organic light—emitting diodes(OLEDs)，having excellent properties of low driving voltage and bright emission，have been extensively studied due to their possible applications for flat panel color displays．Recently，Organic／organometallic complexes with spiro—type structure have attracted a considerable attention．With research deepening,SOltle questions concerning material optimum and emission mechanism，such as molecular architecture， charge transport，relation between electronic and photophysical properties，become increasing important． In the present work，the relations between electronic structure and spectroscopic features of spiro-type organic／organometallic complexes have been investigated by quantum chemistry calculations，The results suggest new theoretical basis and direction for design of novel organic mmefials。Our work will focus on four aspects： 1． Electronic structure and photophysical properties of oligothiophene一 (9，9-spirofluorene)一oligothiophene with spiro—linked structure characters have been studies systematically．The dependence relations between thiophene chain length and energies gaps， excitation energies and singlet-triplet splitting have been elucidated．The conjugated bond relaxation of singly oxidation state and triplet shows that these complexes have obvious trap- barrier-trap form，a kind of new polaron distribution form．HOMO-LUMO gaps decreased with increasing chain length．The TDDFT and ZINDO results indicated that with the increase of the number of thiophene tings，the maximum absorption wavelength is redshifled and the oscillat