联吡啶RuⅡ/Ⅲ配合物二阶非线性光学性质的理论研究

doi:10.7503/cjcu20180465

摘要/Abstract

摘要：

采用密度泛函理论(DFT) 方法对联吡啶Ru^Ⅱ/Ⅲ配合物的几何结构、氧化还原性质、 UV-Vis光谱及二阶非线性光学(NLO) 性质进行计算. 研究结果表明, 醌基的引入能够有效增大第一超极化率(β_tot) 值, 但醌基在氮苯基上位置的改变对β_tot值影响不大. 分子轨道和自旋密度分布分析结果表明, 金属Ru^Ⅱ和副配体均能成为氧化中心, 并且氧化中心位置不同, 会导致配合物氧化态的电荷转移形式产生差别, 进而改变氧化态的β_tot值. 氧化态配合物1b和2b的β_tot值减小, 而配合物3b和4b的β_tot值显著增大, 超瑞利散射方法计算的第一超极化率(β_HRS) 值也符合此规律. 含时密度泛函理论(TD-DFT) 结果表明, 配合物本征态主要是金属到配体的电荷转移(MLCT/ML'CT), 而氧化态则是配体到金属的电荷转移(LMCT/L'MCT), 给、受体发生明显改变. 因此, 通过改变副配体的种类及氧化还原反应, 可有效调节这类联吡啶Ru^Ⅱ/Ⅲ配合物的二阶NLO响应.

关键词: 金属Ru^Ⅱ/Ⅲ配合物;, 氧化还原, 二阶非线性光学性质, 密度泛函理论

Abstract:

The geometry structures, redox properties, UV-Vis electronic absorption spectra and second-order nonlinear optical(NLO) properties of Ru^Ⅱ/Ⅲ-bipyridyl complexes were investigated by density functional theory(DFT). The results present that the introduction of anthraquinone ligands can effectively increase the first hyperpolarizabilities(β_tot) values, but the position of anthraquinone ligands on the nitrogen phenyl group has little effect on the β_tot values. The analysis of molecular orbital and spin density distributions illustrates that both of the metal Ru^Ⅱ and ancillary ligands can serve as the oxidation center of eigenstates. The difference in the oxidation center has a influence on the charge transfer mode, thus affect the β_tot values of oxidized forms. The β_tot values of oxidation states complexes 1b and 2b were decreased whereas the β_tot values of the complexes 3b and 4b enhance dremarkably. The first hyperpolarizabilities(β_HRS) calculated by the Hyper-Rayleigh Scattering method also comply with this phenomenon. Time-dependent density functional(TD-DFT) results indicate that the eigenstates are mainly performed metal-to-ligand charge transfer(MLCT/ML'CT) mode, while the oxidation states complexes are ligand-to-metal charge transfer(LMCT/L'MCT). This is resulting from the inverse changes in donors and acceptors. Therefore, for such Ru^Ⅱ/Ⅲ-bipyridyl complexes, second-order NLO properties can be effectively regulated by the change of ancillary ligands and redox reactions.

Key words: Ruthenium^Ⅱ/Ⅲ complex;, Redox reaction, Second-order nonlinear optical(NLO) property, Density functional theory

中图分类号:

O641

TrendMD:

李想, 王慧莹, 王洪强, 叶近婷, 仇永清. 联吡啶Ru^Ⅱ/Ⅲ配合物二阶非线性光学性质的理论研究. 高等学校化学学报, 2018, 39(10): 2221.

LI Xiang,WANG Huiying,WANG Hongqiang,YE Jinting,QIU Yongqing. Theoretical Studies on the Second-order Nonlinear Optical Properties of Ru^Ⅱ/Ⅲ Complexes of Bipyridyl^†. Chem. J. Chinese Universities, 2018, 39(10): 2221.

图/表 8

Fig.1 Geometric structures for complexes 1a—4a

Table 1 Selected bond distances and bond angles for complexes

Complex	d(Ru—N1)/ nm	d(Ru—N2)/ nm	d(Ru—N3)/ nm	d(Ru—N4)/ nm	d(Ru—N5)/ nm	d(Ru—N6)/ nm	∠N4—Ru—N5/ (°)	∠N5—Ru—N6/ (°)
1a	0.21777	0.20924	0.20944	0.20901	0.21206	0.21142	85.12	77.60
1b	0.21855	0.20870	0.20939	0.20973	0.21228	0.21253	83.38	77.22
2a	0.21129	0.21158	0.21031	0.21012	0.21012	0.21030	89.22	77.93
2b	0.21151	0.21146	0.21106	0.21035	0.21043	0.21105	88.55	77.86
3a	0.21692	0.20917	0.20937	0.20922	0.21207	0.21142	84.97	77.55
3b	0.21747	0.20863	0.20935	0.21007	0.21232	0.21272	83.12	77.22
4a	0.21134	0.21133	0.21031	0.21013	0.21013	0.21031	89.28	77.95
4b	0.21151	0.21150	0.21081	0.21070	0.21070	0.21082	86.75	77.93

Fig.2 Highest occupied molecular orbitals(HOMO) diagram for complexes 1a—4a and spin densities distribution for complexes 1b—4b

Fig.3 UV-Vis spectra of the complexes along with electron density difference maps(EDDM) corresponding to the most intense electronic transitions(A) 1a; (B) 1b; (C) 2a; (D) 2b; (E) 3a; (F) 3b; (G) 4a; (H) 4b. fos: Oscillator strengths.

Table 2 Calculated spectroscopic data of all studied complexes

Complex	λ/nm	E/eV	f_os	Major contributions^*
1a	563(546)^[19]	2.20	0.0965	H-1→L(60%), H-2→L(31%)
	408(390)^[19]	3.03	0.1130	H-2→L+2(29%), H-1→L+2(24%), H-1→L+4(22%), H-2→L+4(14%)
2a	558(440)^[19]	2.22	0.0310	H-1→L(98%)
	421(395)^[19]	2.95	0.1327	H-2→L+3(40%), H-1→L+4(35%), H-2→L+2(17%)
3a	493(520)^[19]	2.52	0.1037	H-1→L(64%), H-2→L(23%)
	413(420)^[19]	3.00	0.1266	H-2→L+1(46%), H-1→L+2(27%), H-1→L+1(16%)
4a	422(452)^[19]	2.94	0.1298	H-2→L+2(47%), H-1→L+3(36%), H-2→L+1(14%)
	340(350)^[19]	3.64	0.1797	H-4→L(69%), H-3→L+4(24%)
1b	461	2.69	0.1625	βH→ βL+1(27%), αH→αL(26%), βH-1→βL+1(20%), αH-1→αL(19%)
	351	3.53	0.1133	αH-9→αL(29%), βH-10→βL+1(29%)
2b	387	3.20	0.1578	βH-2→ βL+1(41%), αH-2→αL(37%)
	317	3.92	0.3253	βH-1→βL+5(22%), αH-1→αL+4(19%)
3b	420	2.95	0.0104	βH-11→βL(87%)
	389	3.19	0.0046	βH-14→βL(62%)
4b	701	1.77	0.0030	βH-3→βL(81%), βH-6→βL(13%)
	592	2.09	0.0073	βH-7→ βL(80%), βH-5→ βL(15%)

Fig.4 Molecular orbitals related to the dominant electron transitions of the complexes 2a and 2b

Table 3 Individual components of first hyperpolarizabilities and total effective values

Complex	Method	β_x/a. u.	β_y/a. u.	β_z/a. u.	β_tot/a. u.
1a	CAM-B3LYP	3348.38	-189.06	-1397.25	3633.14
	ωB97XD	3351.94	-492.59	-1380.73	3658.49
1b	CAM-B3LYP	-46.18	3304.03	-1239.64	3529.22
	ωB97XD	69.70	2995.24	-1057.94	3177.36
2a	CAM-B3LYP	706.68	-2659.16	168.53	2756.61
	ωB97XD	629.65	-2639.39	147.26	2717.44
2b	CAM-B3LYP	67.53	878.76	-4.56	881.37
	ωB97XD	-18.38	673.47	-206.74	704.72
3a	CAM-B3LYP	-149.84	-171.04	-579.01	622.06
	ωB97XD	7.59	-239.25	-551.49	601.20
3b	CAM-B3LYP	-789.04	2143.38	-774.23	2411.66
	ωB97XD	-721.11	1831.16	-736.26	2101.25
4a	CAM-B3LYP	-16.54	1372.57	8.84	1372.69
	ωB97XD	-15.32	1135.35	6.40	1135.47
4b	CAM-B3LYP	-96.98	3738.85	149.25	3743.09
	ωB97XD	-20.99	3655.68	253.09	3664.49

Table 4 βHRS, βJ values, as well as the ρ and DR of all complexes calculated at the CAM-B3LYP/6-31G*/SDD level in acetonitrile, using wavelengths of 1340, 1460, and 1907 nm

λ/nm	Complex	β_HRS	DR	$β J = 1$	$β J = 3$	ρ
1340	1a	1971	4.052	3431.36	3648.75	1.06
	2a	2294	2.653	3156.94	5658.11	1.79
	3a	945	1.672	586.81	2926.60	4.99
	4a	996	1.575	415.97	3164.49	7.61
	1b	1369	5.988	2687.59	1681.42	0.63
	2b	263	1.632	144.69	824.15	5.70
	3b	984	6.967	1995.84	929.46	0.47
	4b	1118	6.595	2242.47	1176.88	0.52
1460	1a	1720	3.931	2958.42	3262.73	1.06
	2a	2080	2.595	2811.85	5192.71	1.85
	3a	854	1.646	491.94	2664.96	5.42
	4a	923	1.604	452.36	2909.57	6.43
	1b	1225	6.003	2405.38	1498.92	0.62
	2b	248	1.712	169.81	761.05	4.48
	3b	868	6.948	1759.72	824.75	0.47
	4b	1057	6.621	2122.31	1104.83	0.52
1907	1a	1323	3.677	2211.28	2640.79	1.19
	2a	1701	2.48	2211.21	4355.04	1.97
	3a	704	1.618	366.37	2210.52	6.03
	4a	792	1.679	501.08	2448.21	4.89
	1b	1002	5.934	1962.49	1246.42	0.64
	2b	223	1.963	216.13	643.79	2.98
	3b	704	6.696	1417.76	721.08	0.51
	4b	943	6.666	1896.26	973.62	0.51

Table 4 βHRS, βJ values, as well as the ρ and DR of all complexes calculated at the CAM-B3LYP/6-31G*/SDD level in acetonitrile, using wavelengths of 1340, 1460, and 1907 nm

λ/nm	Complex	β_HRS	DR	$β J = 1$	$β J = 3$	ρ
1340	1a	1971	4.052	3431.36	3648.75	1.06
	2a	2294	2.653	3156.94	5658.11	1.79
	3a	945	1.672	586.81	2926.60	4.99
	4a	996	1.575	415.97	3164.49	7.61
	1b	1369	5.988	2687.59	1681.42	0.63
	2b	263	1.632	144.69	824.15	5.70
	3b	984	6.967	1995.84	929.46	0.47
	4b	1118	6.595	2242.47	1176.88	0.52
1460	1a	1720	3.931	2958.42	3262.73	1.06
	2a	2080	2.595	2811.85	5192.71	1.85
	3a	854	1.646	491.94	2664.96	5.42
	4a	923	1.604	452.36	2909.57	6.43
	1b	1225	6.003	2405.38	1498.92	0.62
	2b	248	1.712	169.81	761.05	4.48
	3b	868	6.948	1759.72	824.75	0.47
	4b	1057	6.621	2122.31	1104.83	0.52
1907	1a	1323	3.677	2211.28	2640.79	1.19
	2a	1701	2.48	2211.21	4355.04	1.97
	3a	704	1.618	366.37	2210.52	6.03
	4a	792	1.679	501.08	2448.21	4.89
	1b	1002	5.934	1962.49	1246.42	0.64
	2b	223	1.963	216.13	643.79	2.98
	3b	704	6.696	1417.76	721.08	0.51
	4b	943	6.666	1896.26	973.62	0.51

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