含噻吩环的吡啶Ru(II)配合物的电子结构和非线性光学性质
含噻吩环的吡啶Ru(II)配合物的电子结构和非线性光学性质
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DOI：
10.3866/pku.whxb20110236
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发表时间：
2011-01
期刊：
影响因子：
--
通讯作者：
仇永清
中科院分区：
文献类型：
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作者：
仇永清
采用密度泛函理论（DFT）B3 LYP方法研究了一系列含噻吩环的吡啶基钌（II）配合物的电子结构和非线性光学性质，结果表明：[RuII（NH3）5L]2+配位原子与金属离子之间没有形成稳定的化学键（L：含噻吩环的有机基团）络合物。然而，CO取代NH_3后，Ru（II）与碳原子形成稳定的σ-π配位键，这降低了受体基团的未占轨道能量。由于噻吩环数目的增加，系统共轭度增加，这有利于分子内的电荷转移，所有体系的极化率α和一阶超极化率β值都因上述原因而显著提高，根据前线分子轨道，CO的引入使[RuII（CO）5L]2+配合物的β值比[RuII（NH 3）5L] 2+类似物提高了约7倍，这可归因于配体-金属电荷转移（LMCT）。
Density functional theory(DFT) with the B3LYP functional was used to investigate the electronic structures and nonlinear optical(NLO) properties of a series of pyridine-based Ru(II) complexes containing thiophene rings.The results indicate that stable chemical bonds do not form between the coordinated atoms and the metal ion for [RuII(NH3)5L]2+(L:organic groups containing the thiophene ring) complexes.However,strong donor-acceptor(D-A) interactions do exist.The Ru(II) and carbon atoms form stable σ-π coordinated bonds after NH3 is substituted by CO,which decreases the unoccupied orbital energies of the acceptor groups.The degree of system conjugation increases because of an increase in the number of thiophene rings,which is favorable for intramolecule charge transfer.The polarizability α and the first-order hyperpolarizability β values of all the systems are enhanced significantly because of the abovementioned reasons.According to the frontier molecular orbitals,the contribution to the second-order NLO coefficient mainly comes from an intraligand charge transfer(ILCT) and an interligand charge transfer(LLCT).The introduction of CO increases the β value for the [RuII(CO)5L]2+ complex about seven times compared with the [RuII(NH3)5L]2+ analogue,which can be attributed to a ligand-to-metal charge transfer(LMCT).