Theoretical Study on the Second-order Nonlinear Optical Properties of D-A-D(D') o-Carborane Triads†

doi:10.7503/cjcu20180098

Abstract

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

CLC Number:

O641

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2018, 39(7): 1490.

Figures/Tables 8

References 32

[1]	Nalwa H. S., Appl. Organomet.Chem., 1991, 5(5), 349—377
[2]	Nalwa H. S., Adv. Mater., 1993, 5(5), 341—358
[3]	Taylor J., Caruso J., Newlon A., Englich U., Ruhlandt Senge K., Spencer J. T., Inorg. Chem., 2001, 40(14), 3381—3388
[4]	Zhao X. X., Ma J. P., Dong Y. B., Huang R. Q., Lai T., Cryst. Growth Des., 2007, 7(6), 1058—1068
[5]	Li R. R., Wang H. Q., Wang L., Wu J., Qiu Y. Q., Chem. J. Chinese Universities, 2017, 38(10), 1796—1803
	(李荣荣, 王洪强, 王丽, 吴娟, 仇永清.高等学校化学学报,2017, 38(10), 1796—1803)
[6]	Wu K., Chen C., Appl. Phys. A, 1992, 54(3), 209—220
[7]	Verbiest T., Houbrechts S., Kauranen M., Clays K., Persoons A., J. Mater. Chem., 1997, 7(11), 2175—2189
[8]	Fukui H., Shigeta Y., Nakano M., Kubo T., Kamada K., Ohta K., Champagne B., Botek E., J. Phys. Chem. A, 2011, 115(6), 1117—1124
[9]	Kanis D. R., Ratner M. A., Marks T. J., Chem. Rev., 1994, 94(1), 195—242
[10]	Coe B. J., Jones L. A., Harris J. A., Brunschwig B. S., Asselberghs I., Clays K., Persoons A., J. Am. Chem. Soc., 2003, 125(4), 862—863
[11]	Coe B. J., Foxon S. P., Harper E. C., Raftery J., Shaw R., Swanson C. A., Asselberghs I., Clays K., Brunschwig B. S., Fitch A. G., Inorg. Chem., 2009, 48(4), 1370—1379
[12]	Di Bella S., Chem. Soc.Rev., 2001, 30(6), 355—366
[13]	Mendes P. J., Silva T. J. L., Garcia M. H., Ramalho J. P., Carvalho A. P., J. Chem. Inf. Model., 2012, 52(8), 1970—1983
[14]	Coe B. J., Acc. Chem.Res., 2006, 39(6), 383—393
[15]	Wang C. H., Ma N. N., Sun X. X., Sun S. L., Qiu Y. Q., Liu P. J., J. Phys. Chem. A, 2012, 116(43), 10496—10506
[16]	Wang W. Y., Ma N. N., Wang C. H., Zhang M. Y., Sun S. L., Qiu Y. Q., J. Mol. Graph Modell., 2014, 48, 28—35
[17]	Lachman A., Eur. J. Inorg.Chem., 1900, 33(1), 1030—1034
[18]	Wang H. Q., Wang L., Li R. R., Ye J. T., Chen Z. Z., Chen H., Qiu Y. Q., Xie H. M., J. Phys. Chem. A, 2016, 120(46), 9330—9340
[19]	Ma N. N., Li S. J., Yan L. K., Qiu Y. Q., Su Z. M., Dalton Trans., 2014, 43(13), 5069—5075
[20]	Mukherjee S., Thilagar P., Chem. Commun., 2016, 52(6), 1070—1093
[21]	Fang X. Y., Wang W. Y., Wang J., Li X. Q., Song H. J., Qiu Y. Q., Chem. J. Chinese Universities, 2014, 35(11), 2377—2383
	( 方新燕, 王文勇, 王娇, 李晓倩, 宋洪娟, 仇永清.高等学校化学学报,2014, 35(11), 2377—2383)
[22]	Plesek J., Chem.Rev., 1992, 92(2), 269—278
[23]	Reed C. A., Acc. Chem.Res., 1998, 31(3), 133—139
[24]	Reed C. A., Acc. Chem.Res., 2009, 43(1), 121—128
[25]	Allis D. G., Spencer J. T., J. Organomet. Chem., 2000, 614/615, 309—313
[26]	Allis D. G., Spencer J. T., Inorg.Chem., 2001, 40(14), 3373—3380
[27]	Taylor J., Caruso J., Nevolon A., Englich U., Ruhlandt-senge K., Spencer J. T., Inorg. Chem., 2001, 40(14), 3381—3388
[28]	Fang X. Y., Wang L., Zhu C. L., Wang W. Y., Qiu Y. Q., J. Organomet. Chem., 2016, 801, 54—59
[29]	Kokado K., Chujo Y., J. Org. Chem., 2011, 76(1), 316—319
[30]	Furue R., Nishimoto T., Park I. S., Lee J., Yasuda T., Angew. Chem. Int. Ed., 2016, 55(25), 7171—7175
[31]	Frisch M.J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Montgomery J. A. Jr., Vreven T., Kudin K. N., Burant J. C., Millam J. M., Iyengar S. S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N., Petersson G. A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Klene M., Li X., Knox J. E., Hratchian H. P., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Ayala P. Y., Morokuma K., Voth G. A., Salvador P., Dannenberg J. J., Zakrzewski V. G., Dapprich S., Daniels A. D., Strain M. C., Farkas O., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Ortiz J. V., Cur Q., Baboul A. G., Clifford S., Cioslowski J., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R. L., Fox D. J., Keith T., Al-Laham M. A., Peng C. Y., Nanayakkara A., Challacombe M., Gill P. M. W., Johnson B., Chen W., Wong M. W., Gonzalez C., Pople J. A., Gaussian 09, Revision D. 01, Gaussian Inc.,Wallingford CT, 2009
[32]	Kurtz H. A., Stewart J. J. P., Dieter K. M., J. Comput. Chem., 1990, 11, 82—87

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