马来腈二硫纶和邻菲咯啉二酮镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物的分子内荷移跃迁和光敏性研究

Intramolecular Charge-transfer Transition and Photosensitivity of Nickel (Ⅱ), Copper(Ⅱ) and Zinc (Ⅱ) Complexes of Maleonitriledithiolate and 1, 10-Phenanthrpline-5, 6-dione

研究了标题配合物Ｍ（ｍｎｔ）（ｐｈｅｎ－５，６－ｄｉｏｎｅ）的电子吸收和发射光谱，经分子力学（ＭＭ＋）几何优化再用ＺＩＮＤＯ／Ｓ方法进行了多组态的ＲＨＦ－ＳＣＦ－ＣＩ计算，研究了配合物的激发态。探讨了用配合物掺杂及未掺杂 ＣｄＳ－ＰＶＡ膜的暗电导、光电导和光敏性。发现配合物的光敏性按金属离子顺序Ｃｕ２＋＜Ｎｉ２＋＜Ｚｎ２＋依次增强，并与金属离子对ＬＬ’ＣＴ的影响基本一致。

The intramolecular charge-transfer transition of the title complexes MLL' (M=Ni2+,Cu2+,Zn2+;L= mnt2-, L' = phen-5,6-dione) have been studied by comparison of the electronic absorption and emission spectra with the multiconfiguragion RHF-SCF-CI calculations of ZINDO/S method. The investigation of the photosensitivity has been implemented by the measurements of the dark conductivity and photoconductvity of the doped MLL' (9.8 % )-CdS(90.2%)-PVA films and undoped CdS-PVA film. It has been found that the complexes MLL' exhibit a strong fluorescent emission band in the rabge 420-550nm under ultraviolet light at room temperature. The wavelength and relative intensity of the emission band,as well as the photosensitivity of the MLL' in film, are incremental in the matal ionic order Cu2+＜Ni2+＜Zn2+. It in turns out that the HOMO of the MLL' consists of the orbitals of the ligand mnt2- and the LUMO consits of the orbitals of the ligand phen-5,6-dione and metal ion. The absorption and emission bands at the visible region belong in effect to the intramolecular charge-transfer transitions (LL'CT) from the mut2--to the phen-5,6-dione. The effect of the metal ion in the MLL' on the LL'CT is decreased in the metal ionic order Ni2+>Cu2+>Zn2+.