基于α-肉桂酰环乙烯酮二硫缩酮的一类新型D-A有机发光材料的理论

Theoretical Investigation on Novel Donor-acceptor Materials with Organic Light-emitting Diodes Based on α-Cinnamoyl Cyclic Ketene Dithioacetals

用密度泛函理论B3LYP方法对四种新型D-π-A分子(PKD,NKD,TKD和CKD)进行基态几何构型全优化,计算分子的电离势IP和电子亲和势EA等相关能量。用含时密度泛函(TDDFT)方法计算吸收光谱,用单组态相互作用方法(CIS)优化四种化合物分子的S1激发态结构,分析其能量与发射光谱的关系。根据化合物组成的不同恰当地选择泛函计算分子的发射光谱,并与实验结果对照表明,计算结果比较可靠。

Donor-acceptor （D-A） organic molecule is one of the most important conjugated organic materials, which have attracted much academic and technological research interests. In these compounds the electron-donating and electron-accepting groups are connected through a conjugated linker. Tuning different donor moiety or acceptor moiety in a D-A molecule can modify its physical and chemical properties. A novel family of α-cinnamoyl cyclic ketene dithioacetals （CCKDA） derivatives were synthesized with asymmetrical structure （D-A） in a simple and low-cost way by Claisen-Schmidt condensation reactions between the donor-containing aldehydes and the electron-withdrawing by Peng, Sun, et al. Four novel donor acceptor molecules ： （ E ） -1 -（ 1,3-dithiolan-2-ylidene ） 4-（ 10-ethyl-10H-pbenothiazin.3-yl ） but-3-en-2-one, （ E ） 4- [ 4- （ dimethylamino ） phenyl ] -1 - （ 1,3 -dithiolan-2-ylidene ） but-3 -en-2 -one, （ E ） -4- [ 4- （ diphenylamino） phenyl ] -1 -（ 1,3-dithiolan-2.ylidene ） but-3-en-2-one, （E） -4-（ 9-butyl-9 H-carbazol-3-yl ） -1-（ 1,3-dithiolan-2-ylidene） but-3-en-2-one were studied at the B3LYP/6-31 G（d） level of density functional theory （DFT） and ab initio-HF. Adiabatic and vertical electron affinities, adiabatic and vertical ionizing potential were ob- tained. Absorption spectra were obtained by time-dependent density functional theory（TD-DFT）. CIS/6-31G （d） method was used to calculate the first singlet excited state（ S, ） of the four compounds and to analyze the relationship between their energies and emission spectra. The emission spectra were calculated in solvent and compared with experimental data. According to the different compounds the exchange-correlation （XC） functions were chosen properly, and the reliable emission spectra for PKD,NKD,TKD, CKD were obtained.