D-A-D(D')型邻位碳硼烷三元体系二阶非线性光学性质的理论研究

doi:10.7503/cjcu20180098

摘要/Abstract

摘要：

采用密度泛函理论(DFT)方法对系列具有D-A-D(D')型结构的邻位碳硼烷三元体系的电子结构、第一超极化率和电子光谱等性质进行研究. 结果表明, 碳硼烷具有独特的缺电子特征, 可以作为有效的吸电子基团, 与其桥联不同的供电子取代基Ar, 形成三元体系的电荷转移方向是由Ar基团到碳硼烷. 随着Ar基团供电子能力的增强, 体系相应的第一超极化率值增大, 其中分子7(Ar=N,N-二甲基苯)的β_tot值(39197 a.u.)约为分子1(Ar=间三氟甲基苯, 640 a.u.)的61倍. 分子的电子光谱随Ar基团供电能力的增强发生红移, 并采用二级能级公式对分子的第一超极化率规律给予了解释.

关键词: 邻位碳硼烷, 非线性光学性质, 电荷转移, D-A-D(D')型结构

Abstract:

Density functional theory(DFT) calculations were carried out to investigate the electronic structures, the first hyperpolarizabilities and UV-Vis spectra for a series of o-carborane triads bearing D-A-D(D') features. The results suggest that carborane can be used as an effective electron-withdrawing group due to its electron-deficient structure. For different electron-donating groups, the electron transition is mainly from the Ar group to the carborane moiety. With the enhancement of electron-donating ability of the Ar, the corresponding first hyperpolarizabilities can significantly increase. The β_tot value of molecule 7(Ar=N,N-dimethyl benzene, 39197 a.u.) is almost 61 times as large as that of molecule 1(Ar=m-trifluoromethyl benzene, 640 a.u.). In addition, the absorption spectra of molecules exhibit a remarkably red shift as the electron-donating ability of Ar increased. The two-level model was used to give a reasonable explanation for the first hyperpolarizabilities. Therefore, the second-order nonlinear optical responses of o-carborane triads can be effectively modified by changing the electron-donating capability of bridged Ar substituents.

Key words: o-Carborane, Nonlinear optical(NLO) property, Charge transfer, D-A-D(D') Structure

中图分类号:

O641

TrendMD:

吴娟, 王洪强, 刘晓云, 史志圆, 仇永清. D-A-D(D')型邻位碳硼烷三元体系二阶非线性光学性质的理论研究. 高等学校化学学报, 2018, 39(7): 1490.

WU Juan, WANG Hongqiang, LIU Xiaoyun, SHI Zhiyuan, QIU Yongqing. Theoretical Study on the Second-order Nonlinear Optical Properties of D-A-D(D') o-Carborane Triads^†. Chem. J. Chinese Universities, 2018, 39(7): 1490.

图/表 8

参考文献 32

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Molecule	d(C1—C2)/nm	d(C3—C4)/nm	d(C4—C5)/nm	Molecule	d(C1—C2)/nm	d(C3—C4)/nm	d(C4—C5)/nm
1	0.177(0.173)^[29]	0.121(0.119)^[29]	0.142(0.144)^[29]	5	0.178(0.174)^[29]	0.121(0.120)^[29]	0.142(0.144)^[29]
2	0.177	0.121	0.142	6	0.177	0.121	0.142
3	0.178(0.173)^[29]	0.121(0.119)^[29]	0.142(0.145)^[29]	7	0.179	0.121	0.142
4	0.178(0.173)^[29]	0.121(0.120)^[29]	0.142(0.144)^[29]

Molecule	d(C1—C2)/nm	d(C3—C4)/nm	d(C4—C5)/nm	Molecule	d(C1—C2)/nm	d(C3—C4)/nm	d(C4—C5)/nm
1	0.177(0.173)^[29]	0.121(0.119)^[29]	0.142(0.144)^[29]	5	0.178(0.174)^[29]	0.121(0.120)^[29]	0.142(0.144)^[29]
2	0.177	0.121	0.142	6	0.177	0.121	0.142
3	0.178(0.173)^[29]	0.121(0.119)^[29]	0.142(0.145)^[29]	7	0.179	0.121	0.142
4	0.178(0.173)^[29]	0.121(0.120)^[29]	0.142(0.144)^[29]

Molecule	Charge/e		10³⁰ μ_x/(C·m)	10³⁰ μ_y/(C·m)	10³⁰ μ_z/(C·m)	10³⁰ μ_tot/(C·m)
Molecule	Carborane	Substituent	10³⁰ μ_x/(C·m)	10³⁰ μ_y/(C·m)	10³⁰ μ_z/(C·m)	10³⁰ μ_tot/(C·m)
1	-0.34	0.40	-0.33	2.33	0	2.33
2	-0.34	0.42	0	5.34	-0.33	5.34
3	-0.33	0.39	1.00	30.35	2.00	30.35
4	-0.35	0.42	-1.33	35.69	0.67	35.69
5	-0.35	0.42	-2.33	39.69	1.67	39.69
6	-0.35	0.42	5.67	30.35	-8.34	32.02
7	-0.33	0.40	-2.00	58.71	0.33	58.71
7a	-0.31	0.37	-15.68	31.69	2.33	35.69
7b	-0.35	0.43	16.68	32.36	0.33	36.36
7c	-0.38	0.42	-9.34	44.03	0.67	45.03
7d	-0.43	0.42	-4.34	47.70	0	48.03
7e	-0.36	0.44	4.67	49.37	-5.00	49.70
7f	-0.33	0.40	12.34	48.70	1.33	50.37

Molecule	Charge/e		10³⁰ μ_x/(C·m)	10³⁰ μ_y/(C·m)	10³⁰ μ_z/(C·m)	10³⁰ μ_tot/(C·m)
Molecule	Carborane	Substituent	10³⁰ μ_x/(C·m)	10³⁰ μ_y/(C·m)	10³⁰ μ_z/(C·m)	10³⁰ μ_tot/(C·m)
1	-0.34	0.40	-0.33	2.33	0	2.33
2	-0.34	0.42	0	5.34	-0.33	5.34
3	-0.33	0.39	1.00	30.35	2.00	30.35
4	-0.35	0.42	-1.33	35.69	0.67	35.69
5	-0.35	0.42	-2.33	39.69	1.67	39.69
6	-0.35	0.42	5.67	30.35	-8.34	32.02
7	-0.33	0.40	-2.00	58.71	0.33	58.71
7a	-0.31	0.37	-15.68	31.69	2.33	35.69
7b	-0.35	0.43	16.68	32.36	0.33	36.36
7c	-0.38	0.42	-9.34	44.03	0.67	45.03
7d	-0.43	0.42	-4.34	47.70	0	48.03
7e	-0.36	0.44	4.67	49.37	-5.00	49.70
7f	-0.33	0.40	12.34	48.70	1.33	50.37

Molecule	Method	β_x/a.u.	β_y/a.u.	β_z/a.u.	β_tot/a.u.	Molecule	Method	β_x/a.u.	β_y/a.u.	β_z/a.u.	β_tot/a.u.
1	B3LYP	-48	636	-53	640	7	PBE1PBE	-658	57676	394	57681
	PBE1PBE	-54	968	-82	973	7a	B3LYP	-19321	33987	2825	39197
2	B3LYP	14	3328	-104	3330		PBE1PBE	-17568	31530	2588	36187
	PBE1PBE	15	3390	-107	3392	7b	B3LYP	19209	34941	259	39874
3	B3LYP	377	10601	679	10629		PBE1PBE	17468	32349	236	36765
	PBE1PBE	359	10013	641	10040	7c	B3LYP	-18110	37474	773	41628
4	B3LYP	-584	16883	259	16895		PBE1PBE	-16539	34693	709	38440
	PBE1PBE	-550	15846	243	15858	7d	B3LYP	-14345	40814	0	43262
5	B3LYP	-1537	27273	1080	27338		PBE1PBE	-13029	37816	0	39998
	PBE1PBE	-1433	25404	1005	25464	7e	B3LYP	10294	46256	246	47388
6	B3LYP	-1436	18177	-688	18247		PBE1PBE	9357	42817	223	43828
	PBE1PBE	-1273	16999	-648	17059	7f	B3LYP	17164	39086	149	42689
7	B3LYP	-19321	33987	2825	39197		PBE1PBE	15654	36221	137	39460