SUPPLEMENTARY INFORMATION
Solvothermal syntheses, crystal structures, optical and thermal properties ofnew selenidogermanate and polyselenidogermanate
SHUZHEN LIU, PEIPEI SUN, JINGYU HAN,YUN LIU, YALI SHEN, CHUNYING TANG, HUI SUN* and DINGXIAN JIA
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China.
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*For correspondence
Contents
Table S1. Selected bond lengths (Å) and angles (°) for 1
Table S2.Selected bond lengths (Å) and angles (°) for 2
Table S3.Selected bond lengths (Å) and angles (°) for 3
Table S4.Hydrogen bond lengths (Å) and angles (°) for 1–3
Figure S1. Powder X-Ray diffraction pattern (red) of the polycrystalline sample of compound1 and the simulated pattern (black) base on the single crystal data.
Figure S2. Powder X-Ray diffraction pattern (red) of the polycrystalline sample of compound2and the simulated pattern (black) base on the single crystal data.
Figure S3. Powder X-Ray diffraction pattern (red) of the polycrystalline sample of compound2and the simulated pattern (black) base on the single crystal data.
Figure S4IR spectrum of complex 1.
Figure S5IR spectrum of complex 2.
Figure S6IR spectrum of complex 3.
Figure S7IntermolecularN–H···Se hydrogen bonds between [Ge2Se6]4−anionand [NH4]+, [H2N(CH3)2]+ cations in 1.
Figure S8Crystal structure ofthe [Ni(2)(dien)2]2+ cation in2.Hydrogen atoms are omitted for clarity.
FigureS9Crystal packing diagram of2showing intermolecularhydrogen bonds. Hydrogen atoms of CH2 are omitted for clarity. Cyan tetrahedron: GeSe4.
FigureS10Crystal packing diagram of3showing intermolecularhydrogen bonds. Hydrogen atoms of CH2 are omitted for clarity. Cyan tetrahedron: GeSe4.
FigureS11 TGA curves of complexes 1-3.
Table S1. Selected bond lengths (Å) and angles (°) for 1
Ge(1)–Se(1) / 2.2929(17) / Ge(1)–Se(2) / 2.3121(18)Ge(1)–Se(3) / 2.3935(17) / Ge(1)–Se(3)#1 / 2.3986(16)
Ge(2)–Se(4) / 2.2946(17) / Ge(2)–Se(5) / 2.2949(18)
Ge(2)–Se(6) / 2.4038(17) / Ge(2)–Se(6)#2 / 2.4051(16)
Se(1)–Ge(1)–Se(2) / 113.37(7) / Se(1)–Ge(1)–Se(3) / 110.98(7)
Se(1)–Ge(1)–Se(3)#1 / 110.04(7) / Se(2)–Ge(1)–Se(3) / 113.62(7)
Se(2)–Ge(1)–Se(3)#1 / 112.05(7) / Se(3)–Ge(1)–Se(3)#1 / 95.45(6)
Se(4)–Ge(2)–Se(5) / 113.96(7) / Se(4)–Ge(2)–Se(6) / 112.79(7)
Se(4)–Ge(2)–Se(6)#2 / 109.00(6) / Se(5)–Ge(2)–Se(6)#2 / 112.93(7)
Se(5)–Ge(2)–Se(6) / 111.60(7) / Se(6)–Ge(2)–Se(6)#2 / 95.07(6)
Ge(1)–Se(3)–Ge(1)#1 / 84.55(6) / Ge(2)–Se(6)–Ge(2)#2 / 84.93(6)
Symmetry transformations used to generate equivalent atoms: #1 –x, –y+2, –z+1; #2 –x+1, –y+1, –z+1.
Table S2.Selected bond lengths (Å) and angles (°) for 2
Ge(1)–Se(1) / 2.399(3) / Ge(1)–Se(3) / 2.283(3)Ge(1)–Se(4) / 2.306(3) / Ge(1)–Se(5) / 2.405(3)
Ge(2)–Se(2) / 2.421(3) / Ge(2)–Se(5) / 2.406(3)
Ge(2)–Se(6) / 2.295(3) / Ge(2)–Se(7) / 2.298(3)
Se(1)–Se(2) / 2.325(3) / Ni(1)–N(1) / 2.141(16)
Ni(1)–N(2) / 2.082(15) / Ni(1)–N(3) / 2.104(15)
Ni(1)–N(4) / 2.110(15) / Ni(1)–N(5) / 2.102(16)
Ni(1)–N(6) / 2.104(16) / Ni(2)–N(7) / 2.107(14)
Ni(2)–N(8) / 2.081(15) / Ni(2)–N(9) / 2.149(15)
Ni(2)–N(10) / 2.120(14) / Ni(2)–N(11) / 2.076(14)
Ni(2)–N(12) / 2.142(14)
Se(1)–Ge(1)–Se(3) / 97.65(10) / Se(1)–Ge(1)–Se(4) / 115.94(10)
Se(1)–Ge(1)–Se(5) / 104.65(10) / Se(3)–Ge(1)–Se(4) / 113.51(10)
Se(3)–Ge(1)–Se(5) / 116.43(11) / Se(4)–Ge(1)–Se(5) / 108.28(10)
Se(2)–Ge(2)–Se(5) / 102.87(10) / Se(2)–Ge(2)–Se(6) / 112.80(10)
Se(2)–Ge(2)–Se(7) / 100.72(10) / Se(5)–Ge(2)–Se(6) / 112.94(10)
Se(5)–Ge(2)–Se(7) / 110.19(10) / Se(6)–Ge(2)–Se(7) / 115.92(11)
Se(2)–Se(1)–Ge(1) / 103.75(10) / Se(1)–Se(2)–Ge(2) / 102.27(10)
Ge(1)–Se(5)–Ge(2) / 106.33(9) / N(1)–Ni(1)–N(2) / 82.2(6)
N(1)–Ni(1)–N(3) / 90.1(7) / N(1)–Ni(1)–N(4) / 177.1(6)
N(1)–Ni(1)–N(5) / 98.7(6) / N(1)–Ni(1)–N(6) / 89.0(7)
N(2)–Ni(1)–N(3) / 82.9(6) / N(2)–Ni(1)–N(4) / 95.3(6)
N(2)–Ni(1)–N(5) / 178.8(6) / N(2)–Ni(1)–N(6) / 98.3(7)
N(3)–Ni(1)–N(4) / 90.9(6) / N(3)–Ni(1)–N(5) / 96.4(6)
N(3)–Ni(1)–N(6) / 178.4(7) / N(4)–Ni(1)–N(5) / 83.8(6)
N(4)–Ni(1)–N(6) / 90.0(7) / N(5)–Ni(1)–N(6) / 82.5(6)
N(7)–Ni(2)–N(8) / 83.0(5) / N(7)–Ni(2)–N(9) / 91.9(6)
N(7)–Ni(2)–N(10) / 178.2(6) / N(7)–Ni(2)–N(11) / 95.2(5)
N(7)–Ni(2)–N(12) / 89.2(6) / N(8)–Ni(2)–N(9) / 82.2(6)
N(8)–Ni(2)–N(10) / 98.8(6) / N(8)–Ni(2)–N(11) / 177.4(6)
N(8)–Ni(2)–N(12) / 99.3(6) / N(9)–Ni(2)–N(10) / 88.8(6)
N(9)–Ni(2)–N(11) / 96.0(6) / N(9)–Ni(2)–N(12) / 178.3(6)
N(10)–Ni(2)–N(11) / 83.1(6) / N(10)–Ni(2)–N(12) / 90.1(6)
N(11)–Ni(2)–N(12) / 82.5(6)
Table S3.Selected bond lengths (Å) and angles (°) for 3
Ge(1)–Se(1) / 2.288(2) / Ge(1)–Se(2) / 2.259(2)Ge(1)–Se(3) / 2.335(3) / Ge(1)–Se(3)#1 / 2.338(3)
Se(1)–Ni(1) / 2.666(2) / Ni(1)–N(1) / 2.164(11)
Ni(1)–N(2) / 2.169(11) / Ni(1)–N(3) / 2.144(11)
Ni(1)–N(4) / 2.136(11) / Ni(1)–N(5) / 2.118(11)
Se(1)–Ge(1)–Se(2) / 114.78(8) / Se(1)–Ge(1)–Se(3) / 112.11(9)
Se(1)–Ge(1)–Se(3)#1 / 110.87(9) / Se(2)–Ge(1)–Se(3) / 109.08(9)
Se(2)–Ge(1)–Se(3)#1 / 113.01(9) / Se(3)–Ge(1)–Se(3)#1 / 95.38(9)
Ge(1)–Se(1)–Ni(1) / 111.02(8) / Ge(1)–Se(3)–Ge(1)#1 / 84.62(9)
N(1)–Ni(1)–N(2) / 77.1(5) / N(1)–Ni(1)–N(3) / 143.0(5)
N(1)–Ni(1)–N(4) / 87.7(4) / N(1)–Ni(1)–N(5) / 96.1(5)
N(2)–Ni(1)–N(3) / 77.6(5) / N(2)–Ni(1)–N(4) / 113.2(5)
N(2)–Ni(1)–N(5) / 166.8(5) / N(3)–Ni(1)–N(4) / 78.0(5)
N(3)–Ni(1)–N(5) / 113.4(5) / N(4)–Ni(1)–N(5) / 77.3(5)
N(1)–Ni(1)–Se(1) / 110.8(3) / N(2)–Ni(1)–Se(1) / 81.9(3)
N(3)–Ni(1)–Se(1) / 91.7(3) / N(4)–Ni(1)–Se(1) / 158.8(3)
N(5)–Ni(1)–Se(1) / 90.2(3)
Symmetry transformations used to generate equivalent atoms: #1 –x+1/2,–y+1/2,–z+1/2.
Table S4.Hydrogen bond lengths (Å) and angles (°) for 1–3
D–H···A / d(H···A) / d(D···A) / <(DHA)1
N(1)–H(1A)···Se(2)#1 / 2.67 / 3.502(12) / 154.4
N(1)–H(1B)···.Se(2)#2 / 2.60 / 3.438(12) / 155.2
N(2)–H(2B)···Se(1)#3 / 2.64 / 3.475(12) / 154.8
N(3)–H(1H)···Se(2) / 2.93 / 3.476(10) / 121.3
N(3)–H(1G)···.Se(4)#4 / 2.86 / 3.444(11) / 124.8
N(3)–H(1F)···Se(5)#5 / 2.74 / 3.403(11) / 133.2
N(4)–H(4D)···Se(1)#3 / 2.79 / 3.476(11) / 134.7
N(4)–H(4G)···Se(1)#5 / 2.78 / 3.511(12) / 139.6
N(4)–H(4F)···Se(2)#4 / 2.73 / 3.465(11) / 140.3
N(4)–H(4E)···Se(5) / 2.48 / 3.346(11) / 168.1
2
N(1)–H(1B)···Se(2) / 2.74 / 3.457(17) / 136.6
N(2)–H(2)···Se(7)#1 / 2.90 / 3.752(15) / 155.2
N(3)–H(3B)···Se(6)# 2 / 2.86 / 3.629(16) / 143.3
N(3)–H(3A)···Se(7) / 2.74 / 3.610(15) / 161.3
N(4)–H(4B)···.Se(6)# 2 / 2.68 / 3.580(16) / 172.9
N(4)–H(4A)···Se(7)#1 / 2.67 / 3.552(16) / 163.0
N(5)–H(5)···.Se(6) / 2.63 / 3.516(15) / 160.9
N(6)–H(6B)···Se(2)#1 / 2.66 / 3.434(17) / 143.5
N(6)–H(6A)···Se(4)#1 / 2.57 / 3.459(17) / 166.0
N(7)–H(7B)···Se(3)#3 / 2.81 / 3.662(15) / 156.1
N(7)–H(7A)···.Se(6)#3 / 2.68 / 3.585(14) / 172.5
N(8)–H(8)···Se(4)#1 / 2.59 / 3.473(13) / 161.8
N(9)–H(9A)···Se(3)#3 / 2.63 / 3.505(16) / 161.0
N(9)–H(9B)···Se(4)#4 / 2.79 / 3.693(16) / 174.0
N(10)–H(10A)···Se(3)#1 / 2.70 / 3.518(15) / 150.3
N(11)–H(11)···Se(3)#3 / 2.91 / 3.754(15) / 153.1
N(12)–H(12B)···Se(3)#1 / 2.91 / 3.681(14) / 143.0
3
N(1)–H(1A)···Se(2)#1 / 2.72 / 3.547(12) / 151.7
N(1)–H(1B)···Se(2)#2 / 2.74 / 3.634(11) / 168.3
N(3)–H(3)···Se(1)#3 / 2.79 / 3.654(12) / 156.1
N(4)–H(4)···Se(2)#2 / 2.58 / 3.401(12) / 149.5
N(5)–H(5A)···Se(2)#1 / 2.71 / 3.563(14) / 157.4
Symmetry transformations used to generate equivalent atoms: For 1: #1 –x+1/2,y–1/2,–z+3/2; #2 x,y–1,z; #3 x+1,y,z; #4 –x+1,–y+2,–z+1; #5 –x+1,–y+1,–z+1. For 2: #1 x, –y+1/2, z+1/2; #2 –x, –y, –z+1; #3 x, y+1, z; #4 –x+1, y+1/2, –z+1/2. For 3: #1–x+1/2,–y+1/2,–z+1/2; #2 –x+1/4, y+1/4, z+1/4.
Figure S1. Powder X-Ray diffraction pattern (red) of the polycrystalline sample of compound1 and the simulated pattern (black) base on the single crystal data.
Figure S2. Powder X-Ray diffraction pattern (red) of the polycrystalline sample of compound2and the simulated pattern (black) base on the single crystal data.
Figure S3. Powder X-Ray diffraction pattern (red) of the polycrystalline sample of compound2and the simulated pattern (black) base on the single crystal data.
Figure S4IR spectrum of complex 1.
Figure S5IR spectrum of complex 2.
Figure S6IR spectrum of complex 3.
Figure S7IntermolecularN–H···Se hydrogen bonds between [Ge2Se6]4−anionand [NH4]+, [H2N(CH3)2]+ cations in 1.
Figure S8Crystal structure ofthe [Ni(2)(dien)2]2+ cation in2. Hydrogen atoms are omitted for clarity.
FigureS9.Crystal packing diagram of2showing intermolecularhydrogen bonds. Hydrogen atoms of CH2 are omitted for clarity. Cyan tetrahedron: GeSe4.
FigureS10.Crystal packing diagram of3showing intermolecularhydrogen bonds. Hydrogen atoms of CH2 are omitted for clarity. Cyan tetrahedron: GeSe4.
FigureS11. TGA curves of complexes 1-3.