荧光分子器件均二苯代乙烯-4冠醚的含时密度泛函理论研究（英文）

Stilbene-4 Crown Ether Complexes of Li^+ as Promising Fluorescent Molecular Devices:TD-DFT Investigation in Gas Phase

用DFT与TDDFT方法在B3LYP//6-31+G*水平上讨论了发色团均二苯代乙烯冠醚衍生物与Li+荧光作用.计算结果表明,均二苯代乙烯-4对Li+有强荧光响应.与Li+作用后,两种异构体呈现出不同的荧光效应:顺式的荧光光谱发生了蓝移,并伴随有荧光增强效应;而反式化合物的荧光光谱发生了红移,且伴随着荧光猝灭效应.此外,配合物的光谱发生了大的斯托克斯位移.

The basic chromophore stilbene derivatives were provided to combine with lithium in gas phase. The geometric parameters and electronic properties of the ground state （ SO I and first excited state （S1）, HOMO-LUMO gaps （DE I, as well as the thermodynamic parameters were determined with the B3LYP functional using 6-3 lq-G（ d）. Additionally, the lowest excitation energies [Eg ）, the maximal ab- sorption wavelength, and the emission spectra were studied, by means of the time-dependent density func- tional theory （TD-DFT}. The calculated results indicated stilbene-4 crown ether was fluorescent response to lithium, while its two isomers showed different fluorescence effect： after bonding with lithium, the spec- trum of （ Z）-isomer was blue shifted accompanied fluorescence enhancement effect; in reverse, the spectrum of （ E）-isomer was red shifted accompanied fluorescence quenching effect. These shifts resulted from the in- tramolecular charge transitions （ICT）. Moreover, the spectra appeared large Stokes shift.