论文总字数：26430字

摘 要

合成并表征了一系列对称的席夫碱铂(II)配合物(scPt1-scPt5)，由乙二胺作为桥联基团并在水杨醛配体上用不同的取代基修饰，并系统研究了它们的光物理性质。在它们的紫外-可见吸收光谱中，所有配合物都表现出高能量¹n-π*和内配体¹π-π*电荷转移。配合物scPt1，scPt2和scPt4在400-475 nm处表现出宽的金属-配体电荷转移(¹MLCT)和配体-配体电荷转移(¹LLCT)吸收带，而配合物scPt3和scPt5的这些吸收带对应于¹MLCT / ¹ILCT转移并混合分子内能量转移(¹ICT)。配合物scPt1，scPt2和scPt4的发射暂定分配为³MLCT / ³LLCT，而scPt5具有的强且无结构的荧光发生峰的发射来自¹ICT的。除scPt3外的所有配合物均显示出从可见光到近红外区域的中等三重态瞬态吸收(TA)，其中可能出现反饱和吸收(RSA)的性质。因此正如非线性透射实验所证明的，在纳秒激光脉冲下它们在532nm处显示出强的反饱和吸收。其中，配合物scPt5的光限幅性能最强，有潜力应用到非线性光学器件

关键词：席夫碱铂配合物；光物理性质；光限幅

A novel Schiff base Pt(II) complexes： Synthesis, characterization and optical properties

ABSTRACT

A series of symmetric Schiff base platinum(II) complexes(scPt1-scPt5), bridged by ethylenediamine and attached different substituents on the salicylaldehyde ligands, were synthesized and characterized, and their photophysical properties were investigated systematically. In their UV-vis absorption spectra, all complexes exhibit high-energy ¹n-π* and intraligand ¹π-π*transitions. Complexes scPt1, scPt2 and scPt4 exhibit board metal-to-ligand charge transfer(¹MLCT)/ligand-to-ligand charge transfer(¹LLCT) absorption bands in the 400-475 nm, while these absorption bands of complexes scPt3 and scPt5 are corresponded to the ¹MLCT/¹ILCT transitions mixed the intramolecular energy transfer (¹ICT). The emission of complexes scPt1, scPt2 and scPt4 are tentatively assigned to the ³MLCT/³ILCT, and the emission of scPt5 includes a strong and structureless fluorescence band from ¹ICT. All complexes except scPt3 all exhibit moderate triplet transient absorption (TA) from the visible to the NIR region, where reverse saturable absorption (RSA) could arise. Therefore, they show strong reverse saturable absorption at 532 nm for nanosecond laser pulses as demonstrated by the nonlinear transmission experiment. Among them, complexe scPt5 shows the strongest reverse saturable absorption performance, which could be used as a kind of optical power limiting(OPL) material potentially.

Key words：Schiff base Pt(II) complexes；Photophysical properties；optical power limiting

目 录

摘要……………………………………………………………………………………………… I

Abstract……………………………………………………………………………………………… II

第一章 文献综述……………………………………………………………………………………… 1

1.1 研究背景…………………………………………………………………………………………1

1.1.1 引言…………………………………………………………………………………………1

1.1.2 光限幅防护机理……………………………………………………………………………1

1.1.2 席夫碱铂金属配合物………………………………………………………………………2

1.2 研究进展 …………………………………………………………………………………………2

1.3 总结………………………………………………………………………………………………5

第二章 实验部分………………………………………………………………………………………6

2.1 前言………………………………………………………………………………………………6

2.2 化合物b1-b5的合成………………………………………………………………………………7

2.3 化合物L1-L5的合成………………………………………………………………………………7

2.4 化合物scPt1-scPt5的合成………………………………………………………………………8

第三章 结果与讨论…………………………………………………………………………………11

3.1 紫外-可见吸收光谱………………………………………………………………………………11

3.2 发射光谱…………………………………………………………………………………………12

3.3 量化计算…………………………………………………………………………………………14

3.4 纳秒瞬态吸收光谱………………………………………………………………………………15

3.5 非线性光学研究…………………………………………………………………………………17

第四章 结论与展望…………………………………………………………………………………18

4.1结论………………………………………………………………………………………………18

4.2展望…………………………………………………………………………………………………18

参考文献…………………………………………………………………………………………………19

致谢…………………………………………………………………………………………………23

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