Supporting information Combination of N-Arylstilbazolium Organic Nonlinear Optical Chromophores with Iodoargentates: Structural Diversities and Optical Properties Yu-Kang Wang, Li-Ming Zhao, Yu-Qing Fu, Zhao Chen, Xiao-Yan Lin, Dao-Hua Wang, Yi Li, Hao-Hong Li, * Zhi-Rong Chen * College of chemistry, Fuzhou University, Fuzhou, Fujian, 350116, China. State Key Laboratory Breeding Base of Photocatalysis, Fuzhou University, Fuzhou 350002, China *Corresponding Authors: lihh@fzu.edu.cn and zrchen@fzu.edu.cn Table S1 Selected bond lengths (Å) and angles ( ) for 1-3 Compound 1 Ag(1)-I(1) 2.8217(16) Ag(1)-I(2) 2.9240(15) Ag(1)-I(1)#2 2.8223(15) Ag(1)-I(2)#2 2.9324(16) Ag(2)-I(2) 3.0399(17) Ag(2)-I(3) 2.7666(15) Ag(2)-I(2)#2 2.9983(16) Ag(2)-I(3)#2 2.7844(16) Ag(1)-Ag(2) 3.148(2) I(1)-Ag(1)-I(1)#2 113.66(6) I(1)-Ag(1)-I(2) 101.93(5) I(1)#2-Ag(1)-I(2) 111.43(5) I(1)-Ag(1)-I(2)#2 109.74(5) I(1)#2-Ag(1)-I(2)#2 101.71(5) I(2)-Ag(1)-I(2)#2 118.86(5) I(3)-Ag(2)-I(3)#2 128.93(6) I(3)-Ag(2)-I(2)#2 110.49(6) I(3)#2-Ag(2)-I(2)#2 102.21(5) I(3)-Ag(2)-I(2) 101.58(5) I(3)#2-Ag(2)-I(2) 100.06(6) I(2)#2-Ag(2)-I(2) 113.25(5) Symmetry codes: #1 x,-y+1/2,z+1/2; #2 x,-y+1/2,z-1/2 Compound 2 Ag(1)-I(1) 2.8217(12) Ag(1)-I(2)#2 2.7629(11) Ag(1)-I(3) 2.8900(14) Ag(1)-I(3)#2 3.1979(13) Ag(2)-I(1) 2.9962(12) Ag(2)-I(2) 2.8482(12) Ag(2)-I(3) 2.9037(11) Ag(2)-I(1)#1 2.8644(14) Ag(1)-Ag(1)#2 3.0004(18) Ag(1)-Ag(2)#2 3.0796(16) Ag(1)-Ag(2) 3.1294(13) I(2)#2-Ag(1)-I(1) 130.13(3) I(2)#2-Ag(1)-I(3) 106.35(3) I(1)-Ag(1)-I(3) 107.46(4) I(2)#2-Ag(1)-I(3)#2 100.11(4) I(1)-Ag(1)-I(3)#2 92.53(3) I(3)-Ag(1)-I(3)#2 121.20(3) I(2)-Ag(2)-I(1)#1 103.87(3) I(2)-Ag(2)-I(3) 105.49(4) I(1)#1-Ag(2)-I(3) 114.54(3) I(2)-Ag(2)-I(1) 129.02(3) I(1)#1-Ag(2)-I(1) 101.78(3) I(3)-Ag(2)-I(1) 102.61(4) Symmetry codes: #1 -x+1,-y+2,-z+2; #2 -x,-y+2,-z+2 Compound 3
Ag(1)-I(1) 2.7665(7) Ag(1)-I(2) 3.1552(8) Ag(1)-I(2)#1 2.8928(8) Ag(1)-I(3)#1 2.8471(7) Ag(2)-I(1) 2.8371(7) Ag(2)-I(2) 2.8434(7) Ag(2)-I(3)#2 2.8470(7) Ag(2)-I(3) 2.9885(7) Ag(1)-Ag(1)#1 2.9473(12) Ag(1)-Ag(2) 3.0576(8) Ag(1)-Ag(2)#1 3.1841(8) I(1)-Ag(1)-I(3)#1 128.31(2) I(1)-Ag(1)-I(2)#1 111.76(2) I(3)#1-Ag(1)-I(2)#1 105.53(2) I(1)-Ag(1)-I(2) 97.49(2) I(3)#1-Ag(1)-I(2) 91.72(2) I(2)#1-Ag(1)-I(2) 121.87(2) I(1)-Ag(2)-I(2) 103.45(2) I(1)-Ag(2)-I(3)#2 112.68(2) I(2)-Ag(2)-I(3)#2 116.16(2) I(1)-Ag(2)-I(3) 129.83(2) I(2)-Ag(2)-I(3) 103.16(2) I(3)#2-Ag(2)-I(3) 92.016(19) Symmetry codes: #1 -x,-y,-z+1; #2 -x+1,-y,-z+1 Table S2 Selected bond lengths (Å) and angles ( ) for 4, 5 Compound 4 Ag(1)-I(1) 2.7954(9) Ag(1)-I(1)#2 2.7954(9) Ag(1)-I(2) 3.2748(3) Ag(1)-I(2)#2 3.3944(3) Ag(2)-I(1) 2.8938(14) Ag(2)-I(2) 3.1103(18) Ag(2)-I(3) 2.7204(16) Ag(2)-I(4) 2.8021(15) Ag(3)-I(2) 3.1444(18) Ag(3)-I(3) 2.7147(16) Ag(3)-I(4)#4 2.8146(15) Ag(3)-I(1)#4 2.9031(15) Ag(1)-Ag(3)#1 3.041(2) Ag(1)-Ag(2)#2 3.050(2) Ag(1)-Ag(2) 3.050(2) Ag(2)-Ag(3)#1 3.183(2) I(1)#2-Ag(1)-I(1) 177.06(13) I(3)-Ag(2)-I(4) 118.18(6) I(3)-Ag(2)-I(1) 114.31(6) I(4)-Ag(2)-I(1) 110.48(5) I(3)-Ag(2)-I(2) 105.26(5) I(4)-Ag(2)-I(2) 113.04(5) I(1)-Ag(2)-I(2) 92.56(4) I(3)-Ag(3)-I(4)#4 118.98(6) I(3)-Ag(3)-I(1)#4 116.98(6) I(4)#4-Ag(3)-I(1)#4 109.86(5) I(3)-Ag(3)-I(2) 104.49(5) I(4)#4-Ag(3)-I(2) 110.66(5) I(1)#4-Ag(3)-I(2) 92.17(4) Symmetry codes: #1 x,y-1,z; #2 -x+1/2,y,-z+1/2; #3 -x+1/2,y-1,-z+1/2;#4 x,y+1,z Compound 5 Ag(1)- I(1) 2.792(3) Ag(1)-I(3) 2.879(2) Ag(1)-I(5) 3.029(3) Ag(1)-I(6) 2.949(3) Ag(2)-I(2) 2.802(2) Ag(2)-I(3) 2.952(2) Ag(2)-I(4) 2.8951(19) Ag(2)-I(6) 2.8624(17) Ag(3)-I(3) 3.225(5) Ag(3)-(4)) 2.904(3) Ag(3)-I(5) 2.780(3) Ag(3)-I(1)#2 2.759(3) Ag(4)-I(4) 3.033(2) Ag(4)-I(7) 2.756(2) Ag(4)-I(2)#2 2.778(2) Ag(4)-I(3)#2 2.897(2) Ag(5)-I(4) 3.044(2) Ag(5)-I(5) 2.845(2) Ag(5)-I(6) 2.841(2) Ag(5)-I(7) 2.782(2) Ag(1)-Ag(2) 3.100(3) Ag(2)-Ag(4)#1 3.170(2) Ag(2)-Ag(5) 3.318(2) Ag(4)-Ag(5) 2.978(2) Ag(4)-Ag(2)#2 3.170(2) I(1)-Ag(1)-I(3) 118.15(9) I(1)-Ag(1)-I(6) 113.12(8) I(3)-Ag(1)-I(6) 114.67(8) I(1)-Ag(1)-I(5) 113.70(9) I(3)-Ag(1)-I(5) 90.80(7) I(6)-Ag(1)-I(5) 103.27(8) I(2)-Ag(2)-I(6) 113.09(7) I(2)-Ag(2)-I(4) 106.97(6) I(6)-Ag(2)-I(4) 103.60(5) I(2)-Ag(2)-I(3) 106.81(6) I(6)-Ag(2)-I(3) 115.09(7) I(4)-Ag(2)-I(3) 111.05(7) I(1)#2-Ag(3)-I(5) 131.55(13) I(1)#2-Ag(3)-I(4) 106.97(10) I(5)-Ag(3)-I(4) 109.62(9) I(1)#2-Ag(3)-I(3) 112.35(12) I(5)-Ag(3)-I(3) 88.65(9) I(4)-Ag(3)-I(3) 103.59(11) I(7)-Ag(4)-I(2)#2 121.26(8) I(7)-Ag(4)-I(3)#2 106.90(8) I(2)#2-Ag(4)-I(3)#2 109.03(7) I(7)-Ag(4)-I(4) 117.82(7) I(2)#2-Ag(4)-I(4) 98.19(7) I(3)#2-Ag(4)-I(4) 101.83(7) I(7)-Ag(5)-I(6) 117.52(7) I(7)-Ag(5)-I(5) 106.34(7) I(6)-Ag(5)-I(5) 111.06(7) I(7)-Ag(5)-I(4) 116.64(7) I(6)-Ag(5)-I(4) 100.45(6) I(5)-Ag(5)-I(4) 104.12(6) Symmetry codes: #1 x-1/2,-y-1/2,z; #2 x+1/2,-y-1/2,z
Table S3 Hydrogen bond details in 4 and 5 (lengths in Å and angles in ) D-H A d(d-h) d(h A) DHA d(d A) Symmetry code 4 C(6)-H(6) I(2) 0.93 2.94 151 3.783(9) 1-x,1-y,1-z C(19)-H(19B) N(3) 0.96 2.53 155 3.42(3) 5 C(20)-H(20) N(3) 0.93 2.47 151 3.32(3) C(29)-H(29) I(2) 0.93 2.96 158 3.841(18) C(31)-H(31) N(3) 0.93 2.53 150 3.37(3) 1/2-x,-1/2+y,1/2+z Table S4. π π stacking interactions in 2 and 5 (lengths in Å and angles in ) Compound Cg(I) Cg(J) Symmetry code Dist. Centroids Dihedral angle CgI_Perp dist. CgJ_Perp dist. 2 Cg(1) Cg(2) 1-x,1-y,1-z 3.548(5) 1.8(4) 3.457(3) 3.457(3) Ring Cg(1): N(1) C(2) C(3) C(4) C(5) C(10) Ring Cg(2): C(13) C(14) C(15) C(16) C(17) C(18) 5 Cg(1) Cg(2) 4465.03 3.530(10) 1.2(8) 3.448(8) 3.432(6) Ring Cg(1): C(9) C(10) C(11) C(12) C(13) C(14) ; Ring Cg(2): N(4) C(20) C(21) C(22) C(23) C(24) Table S5. Calculated dipole moments for polar units in 5 Polar unit X (Deybe) Y (Deybe) Z (Deybe) Magnitude (Deybe) 4- Ag 5 I 9 5.0294-1.9631 3.6460 6.5147 (CEMAS) 2+ 2 pair -2.4237 0.5475-0.9731 2.6685 (a)
(b) Fig. S1 1 H NMR (a) and 13 C NMR (b) spectra of [DAST] I: 1 H NMR (400 MHz, DMSO) δ 8.70 (d, J = 6.4 Hz, 2H), 8.07 (d, J = 6.5 Hz, 2H), 7.93 (d, J = 16.1 Hz, 1H), 7.61 (d, J = 8.7 Hz, 2H), 7.19 (d, J = 16.1 Hz, 1H), 6.78 (d, J = 8.7 Hz, 2H), 4.19 (s, 3H), 3.02 (s, 6H). 13 C NMR (101 MHz, DMSO) δ 153.8 (s), 152.3 (s), 144.8 (s), 142.3 (s), 130.6 (s), 123.0 (s), 122.6 (s), 117.6 (s), 112.4 (s), 46.9 (s).
(a) (b) Fig. S2 1 H NMR (a) and 13 C NMR (b) spectra of [DMAQS] I: 1 H NMR (400 MHz, DMSO) δ 9.13 (d, J = 6.7 Hz, 1H), 9.04 (d, J = 8.5 Hz, 1H), 8.38 8.32 (m, 2H), 8.20 (dd, J = 15.8, 9.0 Hz, 2H), 8.00 (dd, J = 18.6, 11.4 Hz, 2H), 7.88 (d, J = 8.8 Hz, 2H), 6.83 (d, J = 8.9 Hz, 2H), 4.45 (s, 3H), 3.08 (s, 6H). 13 C NMR (101 MHz, DMSO) δ 153.6 (s), 152.8 (s), 147.2 (s), 145.2 (s), 139.3 (s), 135.1 (s), 131.8 (s), 129.0 (s), 126.8 (s), 126.2 (s), 123.5 (s), 119.5 (s), 114.4 (s), 113.6 (s), 112.4 (s), 44.5 (s).
(a) (b) Fig. S3 1 H NMR (a) and 13 C NMR (b) spectra of [DPAS] I : 1 H NMR (400 MHz, DMSO) δ 8.81 (d, J = 6.4 Hz, 2H), 8.17 (d, J = 6.5 Hz, 2H), 7.97 (d, J = 16.2 Hz, 1H), 7.64 (d, J = 8.6 Hz, 2H), 7.42 7.29 (m, 5H), 7.21 7.06 (m, 6H), 6.93 (d, J = 8.6 Hz, 2H), 4.24 (s, 3H). 13 C NMR (101 MHz, DMSO) δ 153.3 (s), 149.9 (s), 146.7 (s),
145.2 (s), 140.9 (s), 130.3 (s), 130.2 (s), 128.5 (s), 125.8 (s), 124.9 (s), 123.4 (s), 121.2 (s), 120.9 (s), 47.2 (s). (a) (b) Fig. S4 1 H NMR (a) and 13 C NMR (b) spectra of [DPTAS] I : 1 H NMR (400 MHz, DMSO) δ 8.78 (d, J = 6.7 Hz,
2H), 8.14 (d, J = 6.8 Hz, 2H), 7.94 (d, J = 16.2 Hz, 1H), 7.59 (d, J = 8.7 Hz, 2H), 7.29 (d, J = 16.2 Hz, 1H), 7.18 (d, J = 8.2 Hz, 4H), 7.01 (d, J = 8.3 Hz, 3H), 6.86 (d, J = 8.7 Hz, 2H), 4.23 (s, 3H), 2.29 (s, 6H). 13 C NMR (101 MHz, DMSO) δ 153.4 (s), 150.3 (s), 145.1 (s), 144.1 (s), 141.1 (s), 134.4 (s), 130.8 (s), 130.1 (s), 127.5 (s), 126.1 (s), 123.2 (s), 120.3 (s), 119.8 (s), 47.1 (s), 21.0 (s). (a)
(b) Fig. S5 1 H NMR and 13 C NMR spectra of [CEMAS] I: 1 H NMR (400 MHz, DMSO) δ 8.72 (d, J = 6.6 Hz, 2H), 8.09 (d, J = 6.7 Hz, 1H), 7.94 (d, J = 16.1 Hz, 1H), 7.62 (d, J = 8.8 Hz, 2H), 7.23 (d, J = 16.2 Hz, 1H), 6.88 (d, J = 8.8 Hz, 2H), 4.20 (s, 3H), 3.79 (t, J = 6.6 Hz, 2H), 3.05 (s, 3H), 2.78 (t, J = 6.6 Hz, 2H). 13 C NMR (101 MHz, DMSO) δ 153.8 (s), 150.5 (s), 144.9 (s), 142.0 (s), 130.7 (s), 123.7 (s), 122.7 (s), 119.9 (s), 118.2 (s), 112.7 (s), 47.7 (s), 46.9 (s), 38.5 (s), 15.6 (s). (a) (b) (c) (d) (e) Fig. S6 The photographs of as-grown crystals: 1 (a), 2(b), 3 (c), 4 (d), 5 (e)
Ag 4 I 8 unit (a) (b) Fig. S7 (a) 1-D (Ag 2 I 3 ) n n- chain built from edge-sharing Ag 4 I 8 unit; (b) Packing diagram of 3 illustrating the organic-inorganic positions
Fig. S8 Powder X-ray diffraction (PXRD) patterns for compounds 1-5
Fig. S9 Band structures of 1 (a), 2 (b), 3 (c), 4 (d) and 5 (e). The Fermi level is set at 0 ev Fig. S10 Total and partial density of states of 2(a), 3(b) and 4(c)