三苯基均三嗪基团调控敏化染料光电性能的理论研究

doi:10.7503/cjcu20200077

摘要/Abstract

摘要：

为了探究更高效率的敏化染料, 将三苯基均三嗪基团引入供体-受体-共轭π桥-受体(D-A-π-A)型WS-4(HB)敏化剂中, 设计了7种新型染料分子, 采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)方法优化了新型敏化剂的几何构型, 分析了分子的基态结构、前线轨道能级、吸收光谱、激发能及分子内电荷转移等相关性质. 结果表明, 三苯基均三嗪可以有效改善以三苯胺为电子给体的染料性能, 其中在三苯基均三嗪上双侧连接三苯胺给体的染料HBL2表现出更低的能隙和光捕捉效率. 利用Multiwfn对染料HBL2电子转移情况进行分析, 结果表明, 三苯基均三嗪不仅可起到电子推拉作用, 还在一定程度上起到供体的作用, 对分子内电荷转移起到促进作用.

关键词: 三苯基均三嗪, 三苯胺, 供体-受体-共轭π桥-受体, 分子内电荷转移

Abstract:

By adding the 2,4,6-triphenyl-s-triazine group into the donor-acceptor-π-acceptor(D-A-π-A) configuration sensitizer, seven kinds of new sensitizers were designed. Then the methods of density functional theory(DFT) and time-dependent density functional theory(TD-DFT) were used to study the geometric con-figuration, front-line orbital energy levels, absorption spectral, excitation energy, intramolecular charge transport and other related properties. The results indicate that the 2,4,6-triphenyl-s-triazine group can effectively improve the performance of dyes, which using triphenylamine as electron donors. The dye HBL2, which attaching triphenylamine to both sides of 2,4,6-triphenyl-s-triazine, has lower band gap and higher light harvesting efficiency(LHE). The electron transfer results of the dye HBL2 analysed by the Multiwfn show that 2,4,6-triphenyl-s-triazine not only acts as electronic push-pull effect, but also acts as a donor under certain conditions. So it can promote the intramolecular charge transfer.

Key words: 2,4,6-Triphenyl-s-triazine, Triphenylamine, Donor-acceptor-π-acceptor(D-A-π-A), Intramolecular charge transfer

中图分类号:

O641

TrendMD:

王琳硕, 李昆杰, 刘玉敏, 赵瑞红, 李青, 钱鑫, 张帆, 薛志伟. 三苯基均三嗪基团调控敏化染料光电性能的理论研究. 高等学校化学学报, 2020, 41(7): 1653.

WANG Linshuo, LI Kunjie, LIU Yumin, ZHAO Ruihong, LI Qing, QIAN Xin, ZHANG Fan, XUE Zhiwei. Theoretical Studies of Triphenyl-s-triazine Groups Regulating Photoelectric Properties of Sensitizing Dyes^†. Chem. J. Chinese Universities, 2020, 41(7): 1653.

图/表 9

参考文献 28

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Dye	HB	HBL0	HBL1	HBL2	HBL3	HBL4	HBL5	HBL6
d(C2—C3)/nm	—	—	0.1479	0.1479	0.1467	0.1478	0.1432	0.1445
d(C6—C7)/nm	0.1472	0.1477	0.1477	0.1477	0.1483	0.1479	0.1482	0.1482
d(C10—C11)/nm	0.1456	0.1457	0.1457	0.1457	0.1478	0.1481	0.1478	0.1478
d(C14—C15)/nm	0.1423	0.1424	0.1424	0.1424	0.1458	0.1416	0.1458	0.1458
D(C1-C2-C3-C4)/(°)	—	—	34.259	33.611	33.126	32.868	51.433	51.206
D(C5-C6-C7-C8)/(°)	-20.936	-34.235	-36.407	-34.712	-34.687	-34.472	-34.547	-34.613
D(C9-C10-C11-C12)/(°)	0.222	1.360	1.994	-0.521	-1.378	-1.305	-1.989	-1.648
D(C13-C14-C15-C16)/(°)	-179.993	-179.847	-179.917	-179.928	-179.996	-179.980	-179.806	-179.983

Dye	HB	HBL0	HBL1	HBL2	HBL3	HBL4	HBL5	HBL6
d(C2—C3)/nm	—	—	0.1479	0.1479	0.1467	0.1478	0.1432	0.1445
d(C6—C7)/nm	0.1472	0.1477	0.1477	0.1477	0.1483	0.1479	0.1482	0.1482
d(C10—C11)/nm	0.1456	0.1457	0.1457	0.1457	0.1478	0.1481	0.1478	0.1478
d(C14—C15)/nm	0.1423	0.1424	0.1424	0.1424	0.1458	0.1416	0.1458	0.1458
D(C1-C2-C3-C4)/(°)	—	—	34.259	33.611	33.126	32.868	51.433	51.206
D(C5-C6-C7-C8)/(°)	-20.936	-34.235	-36.407	-34.712	-34.687	-34.472	-34.547	-34.613
D(C9-C10-C11-C12)/(°)	0.222	1.360	1.994	-0.521	-1.378	-1.305	-1.989	-1.648
D(C13-C14-C15-C16)/(°)	-179.993	-179.847	-179.917	-179.928	-179.996	-179.980	-179.806	-179.983

Dye	λ_max/nm	f	LHE	Dye	λ_max/nm	f	LHE
HB	493.39	1.3014	0.950	HBL3	450.28	1.4807	0.966
HBL0	451.36	1.3980	0.960	HBL4	450.97	1.4895	0.968
HBL1	451.47	1.4828	0.967	HBL5	451.00	1.4117	0.961
HBL2	348.82	1.7387	0.982	HBL6	451.09	1.4578	0.965

Dye	λ_max/nm	f	LHE	Dye	λ_max/nm	f	LHE
HB	493.39	1.3014	0.950	HBL3	450.28	1.4807	0.966
HBL0	451.36	1.3980	0.960	HBL4	450.97	1.4895	0.968
HBL1	451.47	1.4828	0.967	HBL5	451.00	1.4117	0.961
HBL2	348.82	1.7387	0.982	HBL6	451.09	1.4578	0.965

Excited state	D/nm	Sr	t/nm	E_coul/eV	Excited state	D/nm	Sr	t/nm	E_coul/eV
S₀→S₁	0.0334	0.811	-0.2644	3.737	S₀→S₄	0.4765	0.716	-0.1357	1.956
S₀→S₂	0.3881	0.652	-0.0776	1.972	S₀→S₅	1.2596	0.318	0.7675	1.198
S₀→S₃	0.6163	0.680	-0.1122	1.636	S₀→S₆	0.6615	0.632	0.0699	1.611