含长链β-二酮环金属铂配合物的电子光谱和二阶非线性光学性质的理论研究

Theoretical Studies on Electronic Spectra and Second-order Nonlinear Optical Properties of Cyclometalated Platinum Complexes with Long Chain β-Diketonate Ancillary Ligands

在B3LYP/LanL2DZ(6-31++G**)理论水平对标题化合物进行结构优化和电子光谱与二阶非线性光学性质计算.结果显示,重金属的配合导致Pt原子与苯环,吡啶环,β-二酮羰基环构成较大的共轭体系,使得分子由基态到第一激发态的π→π*和n→π*跃迁伴随MLCT电荷转移,对应的最大吸收波长在406nm左右,属于近紫外区,β-二酮碳链的长度对结构和电子光谱影响很小,与实验结果一致.长链β-二酮环金属铂配合物分子具有较好的非线性光学性质.

Theoretical studies on cyclometalated platinum complexes with long chain β-diketonate ancillary ligands have been carried out at B3LYP/LanL2DZ（6-31 ＋ ＋G^＊＊） level to obtain electronic absorption spectra and second-order nonlinear optical properties. The results indicate that a large conjugated system was formed by Pt atom, benzene, pyridine and β-diketonate ancillary ligands, which makes the electronic transition from the ground state to the first excited state （π→π^＊ and n→π^＊） with MLCT transition. The maximal absorption wavelength was obtained at around 406 nm, belonging to near UV. The structure and electronic spectra were little influenced by the length of β-diketonate ancillary alkyl, which is in good agreement with experimental results. The cyclometalated platinum complexes with long chain β-diketonate ancillary ligand molecules display good nonlinear optical properties.