College of Chemistry and Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing University of Technology, Nanjing 210009, PR China.
Spectrochim Acta A Mol Biomol Spectrosc. 2012 Feb;86:20-6. doi: 10.1016/j.saa.2011.09.034. Epub 2011 Oct 4.
The structures and some molecular properties of the complexes M(mnt)(2)(2-) (M=Ni, Pd, Pt and Zn, Cd, Hg; mnt(2-)=deprotonated maleonitriledithiolate) have been studied by using density functional theory (DFT) B3LYP/LanL2DZ level of theory. Computed binding energies show that the sequences of binding strengths are Ni<Pd<Pt and Cd<Hg<Zn. The natural bonding orbitals analyses show that Ni, Pd and Pt gain 1.40e, 1.62e and 1.72e, respectively to their ns, [Formula: see text] and [Formula: see text] orbitals from both ligand mnt(2-) and (n-1)d(yz) of metal ions, while Zn, Cd and Hg complexes gain electrons to their ns orbitals. The absorption spectra of these complexes were obtained by using time-dependent density functional theory associated with polarized continuum model. Comparison of the absorption spectra in acetonitrile solution with those in gas phase show that the solvatochromic effect made the lowest energy absorption red shift by 31, 34 and 44 nm for d(8) metal complexes Ni(mnt)(2)(2-), Pd(mnt)(2)(2-) and Pt(mnt)(2)(2-), respectively, while blue shift by 28, 44, 25 nm for d(10) metal complexes Zn(mnt)(2)(2-), Cd(mnt)(2)(2-) and Hg(mnt)(2)(2-), respectively. The calculated results reproduced the experimental data with the deviations less than 5% for Ni-S stretching vibrational frequencies and less than 3% for other vibrational modes.
采用密度泛函理论（DFT）B3LYP/LanL2DZ 理论水平研究了配合物 M(mnt)(2)(2-)（M=Ni、Pd、Pt 和 Zn、Cd、Hg；mnt(2-)=去质子丙二腈二硫代）的结构和一些分子性质。计算的结合能表明，结合强度的顺序为 Ni<Pd<Pt 和 Cd<Hg<Zn。自然键轨道分析表明，Ni、Pd 和 Pt 分别从配体 mnt(2-)和金属离子(n-1)d(yz)获得 1.40e、1.62e 和 1.72e 到它们的 ns、[Formula: see text] 和 [Formula: see text] 轨道，而 Zn、Cd 和 Hg 配合物获得电子到它们的 ns 轨道。使用与极化连续体模型相关的时间相关密度泛函理论获得了这些配合物的吸收光谱。在乙腈溶液中的吸收光谱与气相中的吸收光谱的比较表明，溶剂化效应使最低能量吸收红移 31、34 和 44nm，分别为 d(8)金属配合物 Ni(mnt)(2)(2-)、Pd(mnt)(2)(2-)和 Pt(mnt)(2)(2-)，而 d(10)金属配合物 Zn(mnt)(2)(2-)、Cd(mnt)(2)(2-)和 Hg(mnt)(2)(2-)的蓝移分别为 28、44 和 25nm。计算结果与实验数据的偏差小于 5%，对于 Ni-S 伸缩振动频率的偏差小于 3%，对于其他振动模式的偏差小于 3%。
