硫代双烯镍近红外染料的合成及性质

Syntheses and Characterization of a Series of Nickel Bis(dithiolene) Near-IR Dyes

该文分别通过安息香路线和二酮路线合成了4种具有不同取代基的硫代双烯镍近红外染料,并考察了染料的物理、光电化学及热稳定性等性质。紫外-可见-近红外(UV-Vis-NIR)吸收光谱测试结果表明,配合物在700～1 100 nm都具有较强的吸收。对化合物的取代基效应及溶剂效应的研究发现:供电子基团导致λmax红移,而吸电子基团导致λmax蓝移,且λmax随着溶剂极性增大而增大。利用循环伏安法和差分脉冲伏安法(CV/DPV)测试了化合物的电化学性质。此外,该文还通过密度泛函理论(DFT)对化合物的HOMO和LUMO能级进行了计算。热失重测试研究表明,合成的化合物具有较好的热稳定性。

Four nickel bis （dithiolene） complexes with different substituent groups were synthesized and characterized. The physical and chemical properties of the complexes were systematically studied. The UV-Vis-NIR spectra demonstrate strong and broad absorptions in the NIR region （700 - 1 100 nm）. The substituent effect and solvent effect of the complexes were investigated. The electron donating substituent results in the red-shifted absorption band, while the electron withdrawing substituent results in the hypsochromic-shifted absorption band. The red-shifted absorption band expanded with the increase of the polarity of the solvent. The electrochemical properties were investigated by both cyclic voltammetry/differential pulse voltammetry （CV/DPV）. Furthermore, the HOMO and LUMO energy levels of the dyes were obtained by density functional theory（DFF） calculations. TG studies reveal good thermal stability of the complexes.