S-1
Supporting Information
Transition
Metal
Complex-Directed
Synthesis
of
Hybrid
Iodoargentates with Single-Crystal-to-Single-Crystal Structural
Transformation and Photocatalytic Properties
Chunying Tang#, Jie Yao#, Yueying Li, Zhuoran Xia, Jianbiao Liu, Chunyang Zhang*
College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation
Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Provincial Key Laboratory of
Clean Production of Fine Chemicals, Shandong Normal University, Jinan 250014, China * Corresponding author. Email: [email protected]
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Table of Contents
1. Tables………...S4 Table S1. The summary of TM complex directed hybrid silver halogenides and the photocatalytic
properties………...………..S4
Table S2. Crystal Data and Structure Refinements of Compounds 1–9………..S6 Table S3. Selected bond lengths (Å) and angles (°) of Compound 1……….S10 Table S4. Selected bond lengths (Å) and angles (°) of Compound 2……….S15 Table S5. Selected bond lengths (Å) and angles (°) of Compound 3……….S17 Table S6. Selected bond lengths (Å) and angles (°) of Compound 4……….S21 Table S7. Selected bond lengths (Å) and angles (°) of Compound 5………...S23 Table S8. Selected bond lengths (Å) and angles (°) of Compound 6……….S25 Table S9. Selected bond lengths (Å) and angles (°) of Compound 7……….S27 Table S10. Selected bond lengths (Å) and angles (°) of Compound 8………...S31 Table S11. Selected bond lengths (Å) and angles (°) of Compound 9………...S35 Table S12. Hydrogen bond lengths (Å) and angles (°) of Compounds 1–9………...S39 2. Figures………...S46 Figure S1. Experimental and simulated powder XRD patterns of compounds 1 (a), 2 (b) and 3 (c)
before and after the visible photocatalysis………...………...S46
Figure S2. Experimental and simulated powder XRD patterns of compounds 4 (a), 5 (b) and 6 (c)
before and after the visible photocatalysis………..S47
Figure S3. Experimental and simulated powder XRD patterns of compounds 7 (a), 8 (b) and 9 (c)
before and after the visible photocatalysis………..S48
Figure S4. IR spectra of compounds 1–3………...S49 Figure S5. IR spectra of compounds 4–6………...S49 Figure S6. IR spectra of compounds 7–9………...S50 Figure S7. Stacked diagram of compound 1 (a) and 4 (b) along c axis………...S50 Figure S8. Time-dependent PXRD patterns of compound 1 with crystallization time from 5 days
to 30 days………...S51
Figure S9. View of the packing structure of compound 7 along the a axis………..S51 Figure S10. Optical diffuse reflectance spectra of compounds 1–9…………..………S52
S-3
Figure S11. Absorption spectra of the CV solution in the presence of compounds 1 (a), 2 (b) and 3
(c) under visible light……….………...S52
Figure S12. Absorption spectra of the CV solution in the presence of compounds 4 (a), 5 (b) and 6
(c) under visible light……….………...S52
Figure S13. Absorption spectra of the CV solution in the presence of compounds 7 (a), 8 (b) and 9
(c) under visible light……….………...S53
Figure S14. Absorption spectra of the RhB solution in the presence of compounds 1 (a), 2 (b) and 3 (c) under visible light……….………S53 Figure S15. Absorption spectra of RhB solution in the presence of compounds 4 (a), 5 (b) and 6 (c)
under visible light……….………S54
Figure S16. Absorption spectra of RhB solution in the presence of compounds 7 (a), 8 (b) and 9 (c)
under visible light……….………S54
Figure S17. Visible light-driven photocatalytic degradations of RhB using compounds 1–9 (a, c and
e), the calculated degradation rate of RhB using compounds 1–9 (b, d and f)………...S55
Figure S18. The radical-trapping experiments using compound 3 for the degradation of CV….S56 Figure S19. Total and partial DOS of compound 5……….S56 References……….S57
S-4
Table S1. The summary of TM complex directed hybrid silver halogenides and the photocatalytic
properties.
Compound formulae Anionic
framework Solvent
Reaction temperature/°C
Photocatalytic propertity Ref
[Y(DMF)8][Ag3(μ3-I)(μ-I)3I2] 0D [Ag3I6]3– DMF rt –––– 1
[Y(DMSO)8][Ag2(μ-I)3I2] 0D [Ag2I5]3– DMSO rt –––– 1
[Y(DMSO)8]2[Ag4(μ3-I)2(μ-I)4I2][I]2 0D [Ag4I8]4– DMSO rt –––– 1
[Y(DMSO)7]4[Ag4(μ3-I)4I4]3 0D [Ag4I8]4– DMSO rt –––– 1
[TM(phen)3]2Ag3I7 (TM = Mn, Fe) 0D [Ag3I7] 4– CH3CN/ HI 140 Visible light driven 2
{[Cu(phen)2]2(Ag2I6)·(DMF)2}n 0D [Ag2I6]4– DMF/HI 50 –––– 3
[Fe(phen)3]Ag2Br4·DMF 0D [Ag2Br4]2– DMSO rt –––– 4
[Fe(phen)2(Cl)2]2Ag2Br4 1D [Ag2Br4]2– DMSO rt
Visible light
driven 4
[Y(DMF)8][Ag6(μ4-I)2(μ3-I)2(μ-I)5] 1D [Ag6I9]3– DMF rt –––– 1
[Co(phen)3](Ag3I5)·2CH3CN 1D [Ag3I5]2– CH3CN 110 UV driven 5
[TM(2,2ʹ-bipy)3]Ag3I5
(M = Mn, Fe, Co, Ni, Zn) 1D [Ag3I5]
2– CH3CN/
HI 140
Visible light
driven 6
{[Ni(2,2ʹ-bipy)(THF)2(H2O)2](Ag10I12)·2DMF}n 1D [Ag10I12]
2– DMF/THF/
HI rt
––––
7 {[Cu(2,2ʹ-bipy)3](Ag5I7)}n 1D [Ag5I7]2–
DMF/THF/ HI rt –––– 7 [Mn(4,4-bipy)(DMF)3(H2O)]Ag5I7 ∙4,4-bipy 1D [Ag5I7]2– DMF/H2O rt –––– 8 [Mn(4,4-bpy)(DMSO)4]2Ag11I15 1D [Ag11I15]4– DMSO/ H2O rt –––– 8
[Mn(4,4-bipy)2(DMSO)2(H2O)2]Ag10I12∙2DMS
O∙2H2O 1D [Ag10I12]2– DMSO/ H2O rt –––– 8 [Mn2
(4,4-bipy)2(DMF)5(DMSO)2(H2O)]Ag10I14∙
2DMF 1D [Ag10I14]4– DMF/ DMSO/ H2O rt –––– 8
[Cu(phen)2(Br)]AgBr2 1D [AgBr2] DMSO rt
Visible light
driven 4
{[Cr(DMSO)6][Ag6I9]·H2O} 1D [Ag6I9]3–
DMSO/ H2O/HI
S-5
[Ni(DMSO)6][Ag5I7] 1D [Ag5I7]2– DMSO/
H2O/HI 80 UV driven 9 [TM(phen)3]2Ag11I15·H2O (TM=Co, Cu) 2D [Ag11I15] 4– CH 3CN 110 UV driven 5 [Mn(phen)3]Ag5I7 2D [Ag5I7]2–
CH3CN/
HI 140
Visible light
driven 2
{[Cu(2,2ʹ-bipy)(DMF)2](Ag7I9)}n 2D [Ag7I9]2– DMF/HI 50 –––– 3
Kx[TM(2,2ʹ-bipy)3]2Ag6I11
(M = Mn, Fe, Co, Ni, Zn; x = 0.89−1) 2D [Ag6I11]
5– CH3CN/
HI 140
Visible light
driven 10
[(Ni(2,2ʹ-bipy)3][H2,2ʹ-bipy]Ag3I6 2D [Ag3I6]3–
CH3CN/
HI 140
Visible light
driven 10
K[TM(2,2ʹ-bipy)3]2Ag6Br11
(M = Ni, Co, Zn, Fe)
2D [Ag6Br11]5– CH3CN/ HBr 140 Visible light driven 11 [TM(2,2ʹ-bipy)3]2Ag13Br17 (M = Ni, Co, Zn) 2D [Ag13Br16]3– CH3CN/ H2O 140 Visible light driven 11
[V(DMSO)5(H2O)][Ag6I8] 2D [Ag6I8]2–
DMSO/ H2O/HI
90 UV driven 9
TM(en)3Ag2I4 (TM = Zn, Ni) 3D [Ag2I4]2– DMF rt –––– 12
[TM(phen)3]2Ag13I17
(TM= Co, Cd) 3D [Ag13I17]
4– DMSO 110 UV driven 5
[TM(phen)3]2Ag13Br17·2DMSO·3H2O
(TM = Fe, Co, Ni)
3D [Ag13Br17]4–
DMSO rt Visible light
driven 4
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Table S2. Crystal Data and Structure Refinements of Compounds 1–9
Compound 1 2 3
CCDC code 1988337 1988338 1988339
Formula C45H45N9O3I4Ag2Co C45H45N9O3I4Ag2Ni C45H45N9O3I4Ag2Zn
Formula weight 1542.17 1541.95 1548.61
Crystal system Triclinic Triclinic Triclinic
Space group P –1 P –1 P –1 a (Å) 13.2925(6) 13.2788 (4) 13.2874 (6) b (Å) 13.3176(4) 13.5999 (6) 13.4157 (5) c (Å) 15.1969(6) 14.8667 (6) 15.1598 (8) α (°) 106.046(3) 109.606 (4) 106.081 (4) β (°) 103.931(4) 100.549 (3) 103.798 (4) γ (°) 94.159(3) 92.716 (3) 94.438 (3) V (Å3) 2481.32(18) 2469.17 (17) 2491.7 (2) Z 2 2 2 T (K) 150 150 150 Dc (g·cm–3) 2.064 2.074 2.064 F(000) 1470 1472 1476 μ (mm–1) 3.649 3.712 3.782 2θmax (°) 50.70 50.70 50.70 Measured reflections 18873 18988 20719 Unique reflections 9061 9024 9103
S-7 Rint 0.0381 0.0344 0.0325 Parameters 619 583 610 R1/wR2, [I>2σ(I)]a 0.0482/0.1243 0.0310/0.0641 0.0501/0.1241 Goodness of fit 1.073 1.029 1.063 Δρmax/Δρmin (e·Å-3 ) 2.00/–1.65 1.00/–1.37 3.11/–2.91 a R1 = ∑||F0| - |Fc||/∑|F0|, wR2 = {∑w[(F0)2 - (Fc)2]2/∑w[(F0)2]2}1/2 Compound 4 5 6 CCDC code 1988340 1988341 1988342 Formula C39H31N7OI5Ag3Co C39H31N7OI5Ag3Ni C39H31N7OI5Ag3 Zn Formula weight 1630.75 1630.53 1637.24
Crystal system Monoclinic Monoclinic Monoclinic
Space group P 21/m P 21/m P 21/m a (Å) 14.5580(5) 14.5615(4) 14.5330(3) b (Å) 22.2687(8) 22.2749(5) 22.2480(3) c (Å) 14.6582(5) 14.6783(4) 14.6506(2) α (°) 90 90 90 β (°) 105.321(4) 105.451(3) 105.464(2) γ (°) 90 90 90 V (Å3) 4583.1(3) 4588.9(2) 4565.49(13) Z 4 4 4 T (K) 233 233 233
S-8 Dc (g·cm–3) 2.257 2.254 2.276 F(000) 2860 2864 2872 μ (mm–1) 5.017 5.060 5.199 2θmax (°) 50.70 58.45 58.60 Measured reflections 37118 41555 36556 Unique reflections 8330 11194 10938 Rint 0.034 0.038 0.033 Parameters 475 475 476 R1/wR2, [I>2σ(I)]a 0.0746/0.2329 0.0866/0.2921 0.0822/0.2709 Goodness of fit 1.080 1.043 1.053 Δρmax/Δρmin (e·Å-3 ) 2.72/–3.56 3.47/–4.14 3.26/–4.19 aR1 = ∑||F 0| - |Fc||/∑|F0|, wR2 = {∑w[(F0)2 - (Fc)2]2/∑w[(F0)2]2}1/2 Compound 7 8 9 CCDC code 1988343 1988344 1988345 Formula C93H97N19O7I12Ag8Co2 C93H97N19O7I12Ag8Ni2 C93H97N19O7I12A g8Zn2 Formula weight 4096.55 4096.07 4109.46
Crystal system Monoclinic Monoclinic Monoclinic
Space group P 21/c P 21/c P 21/c
a (Å) 29.3489(7) 29.0751(5) 29.1088(6)
b (Å) 17.6229(3) 17.5161(3) 17.5255(3)
S-9 α (°) 90 90 90 β (°) 111.628(3) 111.955(2) 112.004(2) γ (°) 90 90 90 V (Å3) 11787.1(5) 11617.4(4) 11654.6(4) Z 4 4 4 T (K) 233 233 233 Dc (g·cm–3) 2.267 2.300 2.300 F(000) 7480 7488 7504 μ (mm–1) 4.768 4.876 4.949 2θmax (°) 50.70 58.48 50.70 Measured reflections 85396 108095 82634 Unique reflections 21552 27897 21277 Rint 0.041 0.055 0.037 Parameters 1237 1237 1237 R1/wR2, [I>2σ(I)]a 0.0478/0.1358 0.0528/0.1352 0.0502/ 0.1456 Goodness of fit 1.089 1.026 1.074 Δρmax/Δρmin (e·Å-3) 1.902/–1.82 1.65/–1.91 3.14/–1.89 aR1 = ∑||F 0| - |Fc||/∑|F0|, wR2 = {∑w[(F0)2 - (Fc)2]2/∑w[(F0)2]2}1/2
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Table S3. Selected bond lengths (Å) and angles (°) of Compound 1.
Ag(1A)–I(1) 3.1414(9) Ag(1A)–I(1)#1 2.7383(9) Ag(1A)–I(2A) 2.877(7) Ag(1A)–I(2B) 2.890(7) Ag(1A)–I(3) 2.8580(9) Ag(1A)–Ag(1A)#1 2.9592(15) Ag(1A)–Ag(1B) 2.083(3) Ag(1A)–Ag(1B)#1 2.084(3) Ag(1A)–Ag(2B) 2.583(4) Ag(1B)–I(1) 2.898(3) Ag(1B)–I(1)#1 2.982(3) Ag(1B)–I(2A) 3.191(6) Ag(1B)–I(2B) 2.969(7) Ag(1B)–I(3)#1 3.054(3) Ag(1B)–Ag(1B)#1 2.933(6) Ag(2A)–I(1) 3.076(4) Ag(2A)–I(2A) 2.902(7) Ag(2A)–I(2B) 3.029(7) Ag(2A)–I(3) 3.019(5) Ag(2A)–I(4A) 2.702(4) Ag(2A)–I(4B) 2.491(5) Ag(2B)–I(1) 2.877(5) Ag(2B)–I(2A) 2.822(8) Ag(2B)–I(2B) 2.932(9) Ag(2B)–I(3) 2.896(6) Ag(2B)–I(4A) 2.984(5) Ag(2B)–I(4B) 2.776(6) Co(1)–N(1) 2.115(6) Co(1)–N(2) 2.166(5) Co(1)–N(3) 2.137(6) Co(1)–N(4) 2.150(5) Co(1)–N(5) 2.146(6) Co(1)–N(6) 2.131(6) I(1)–Ag(1A)–I(1)#1 120.03(3) I(1)–Ag(1A)–I(2A) 93.48(12) I(1)#1–Ag(1A)–I(2A) 119.21(11) I(1)–Ag(1A)–I(2B) 89.59(14) I(1)#1–Ag(1A)–I(2B) 116.63(14) I(1)–Ag(1A)–I(3) 93.34(3) I(1)#1–Ag(1A)–I(3) 115.17(3) I(2A)–Ag(1A)–I(2B) 7.11(16)
S-11 I(2A)–Ag(1A)–I(3) 111.12(9) I(2B)–Ag(1A)–I(3) 117.35(10) Ag(1A)#1–Ag(1A)–Ag(1B) 44.76(9) Ag(1A)#1–Ag(1A)– Ag(1B)#1 44.73(9) Ag(1A)#1–Ag(1A)–Ag(2B) 112.62(12) Ag(1A)#1–Ag(1A)–I(1) 53.24(3) Ag(1A)#1–Ag(1A)–I(1)#1 66.79(3) Ag(1A)#1–Ag(1A)–I(2A) 121.06(10) Ag(1A)#1–Ag(1A)–I(2B) 114.02(10) Ag(1A)#1–Ag(1A)–I(3) 117.09(4) Ag(1B)–Ag(1A)–Ag(1B)#1 89.50(12) Ag(1B)–Ag(1A)–Ag(2B) 105.30(15) Ag(1B)#1–Ag(1A)–Ag(2B) 106.40(16) Ag(1B)–Ag(1A)–I(1) 63.66(9) Ag(1B)–Ag(1A)–I(1)#1 75.03(9) Ag(1B)#1–Ag(1A)–I(1) 66.02(9) Ag(1B)#1–Ag(1A)–I(1)#1 72.46(9) Ag(1B)–Ag(1A)–I(2A) 78.29(12) Ag(1B)–Ag(1A)–I(2B) 71.21(13) Ag(1B)#1–Ag(1A)–I(2A) 159.32(15) Ag(1B)#1–Ag(1A)–I(2B) 154.17(15) Ag(1B)–Ag(1A)–I(3) 156.16(10) Ag(1B)#1–Ag(1A)–I(3) 74.48(9) Ag(2B)–Ag(1A)–I(1) 59.39(12) Ag(2B)–Ag(1A)–I(1)#1 178.83(14) Ag(2B)–Ag(1A)–I(2A) 61.96(17) Ag(2B)–Ag(1A)– I(2B) 64.51(19) Ag(2B)–Ag(1A)–I(3) 64.09(13) I(1)–Ag(1B)–I(1)#1 120.17(10) I(1)–Ag(1B)–I(2A) 92.05(14) I(1)–Ag(1B)–I(2B) 92.92(17) I(1)#1–Ag(1B)–I(2A) 103.34(14) I(1)#1–Ag(1B)–I(2B) 107.23(16) I(1)–Ag(1B)–I(3)#1 105.06(9) I(1)#1–Ag(1B)–I(3)#1 92.73(9) I(2A)–Ag(1B)–I(2B) 5.2(2) I(2A)–Ag(1B)–I(3)#1 146.54(14) I(2B)–Ag(1B)–I(3)#1 141.65(15) Ag(1A)–Ag(1B)– 90.50(12) Ag(1A)–Ag(1B)–Ag(1B)#1 45.27(9)
S-12 Ag(1A)#1 Ag(1A)#1–Ag(1B)– Ag(1B)#1 45.24(9) Ag(1A)–Ag(1B)–I(1) 76.25(10) Ag(1A)–Ag(1B)–I(1)#1 62.53(8) Ag(1A)#1–Ag(1B)–I(1) 64.27(9) Ag(1A)#1–Ag(1B)–I(1)#1 74.29(9) Ag(1A)–Ag(1B)–I(2A) 61.99(12) Ag(1A)–Ag(1B)–I(2B) 67.17(14) Ag(1A)#1–Ag(1B)–I(2A) 148.13(17) Ag(1A)#1–Ag(1B)–I(2B) 151.94(19) Ag(1A)–Ag(1B)–I(3)#1 149.56(14) Ag(1A)#1–Ag(1B)–I(3)#1 64.40(8) Ag(1B)#1–Ag(1B)–I(1) 61.49(11) Ag(1B)#1–Ag(1B)–I(1)#1 58.68(10) Ag(1B)#1–Ag(1B)–I(2A) 105.65(17) Ag(1B)#1–Ag(1B)–I(2B) 110.57(19) Ag(1B)#1–Ag(1B)–I(3)#1 107.77(15) I(1)–Ag(2A)–I(2A) 94.37(13) I(1)–Ag(2A)–I(2B) 88.33(14) I(1)–Ag(2A)–I(3) 91.57(12) I(1)–Ag(2A)–I(4A) 117.85(18) I(1)–Ag(2A)–I(4B) 119.2(2) I(2A)–Ag(2A)–I(2B) 6.48(19) I(2A)–Ag(2A)–I(3) 106.02(17) I(2A)–Ag(2A)–I(4A) 118.7(2) I(2A)–Ag(2A)–I(4B) 116.9(2) I(2B)–Ag(2A)–I(3) 108.58(17) I(2B)–Ag(2A)–I(4A) 120.1(2) I(2B)–Ag(2A)–I(4B) 118.4(3) I(3)–Ag(2A)–I(4A) 122.09(18) I(3)–Ag(2A)–I(4B) 122.8(2) I(4A)–Ag(2A)–I(4B) 1.9(2) I(1)–Ag(2B)–I(2A) 100.67(18) I(1)–Ag(2B)–I(2B) 94.13(17) I(1)–Ag(2B)–I(3) 98.34(16) I(1)–Ag(2B)–I(4A) 115.3(2) I(1)–Ag(2B)–I(4B) 116.6(2) I(2A)–Ag(2B)–I(2B) 6.79(19) I(2A)–Ag(2B)–I(3) 111.6(2) I(2A)–Ag(2B)–I(4A) 112.3(2) I(2A)–Ag(2B)–I(4B) 110.6(3)
S-13 I(2B)–Ag(2B)–I(3) 114.8(2) I(2B)–Ag(2B)–I(4A) 114.2(3) I(2B)–Ag(2B)–I(4B) 112.6(3) I(3)–Ag(2B)–I(4A) 116.8(2) I(3)–Ag(2B)–I(4B) 117.3(2) I(4A)–Ag(2B)–I(4B) 1.8(2) Ag(1A)–Ag(2B)–I(1) 70.01(11) Ag(1A)–Ag(2B)–I(2A) 64.15(17) Ag(1A)–Ag(2B)–I(2B) 62.83(18) Ag(1A)–Ag(2B)–I(3) 62.57(11) Ag(1A)–Ag(2B)–I(4A) 174.5(3) Ag(1A)–Ag(2B)–I(4B) 172.8(3) Ag(1A)–I(1)–Ag(1A)#1 59.97(3) Ag(1A)–I(1)–Ag(1B) 40.09(6) Ag(1A)–I(1)–Ag(1B)#1 39.69(6) Ag(1A)#1–I(1)–Ag(1B) 43.28(7) Ag(1A)#1–I(1)–Ag(1B)#1 42.44(6) Ag(1A)–I(1)–Ag(2A) 54.76(7) Ag(1A)–I(1)–Ag(2B) 50.60(9) Ag(1A)#1–I(1)–Ag(2A) 114.73(7) Ag(1A)#1–I(1)–Ag(2B) 110.56(9) Ag(1B)–I(1)–Ag(1B)#1 59.83(10) Ag(1B)–I(1)–Ag(2A) 83.65(9) Ag(1B)–I(1)–Ag(2B) 80.24(11) Ag(1B)#1–I(1)–Ag(2A) 83.33(10) Ag(1B)#1–I(1)–Ag(2B) 79.55(12) Ag(2A)–I(1)–Ag(2B) 4.18(15) Ag(1A)–I(2A)–Ag(1B) 39.72(10) Ag(1A)–I(2A)–Ag(2A) 59.31(15) Ag(1A)–I(2A)–Ag(2B) 53.89(15) Ag(1B)–I(2A)–Ag(2A) 81.55(18) Ag(1B)–I(2A)–Ag(2B) 76.20(19) Ag(2A)–I(2A)–Ag(2B) 5.67(16) Ag(1A)–I(2B)–Ag(1B) 41.62(12) Ag(1A)–I(2B)–Ag(2A) 57.73(15) Ag(1A)–I(2B)–Ag(2B) 52.66(16) Ag(1B)–I(2B)–Ag(2A) 83.3(2) Ag(1B)–I(2B)–Ag(2B) 78.2(2) Ag(2A)–I(2B)–Ag(2B) 5.35(16) Ag(1A)–I(3)–Ag(1B)#1 41.11(6) Ag(1A)–I(3)–Ag(2A) 58.16(6) Ag(1A)–I(3)–Ag(2B) 53.34(9) Ag(1B)#1–I(3)–Ag(2A) 83.09(9) Ag(1B)#1–I(3)–Ag(2B) 78.06(11)
S-14 Ag(2A)–I(3)–Ag(2B) 5.18(14) Ag(2A)–I(4A)–Ag(2B) 1.7(2) Ag(2A)–I(4B)–Ag(2B) 1.6(2) N(1)–Co(1)–N(2) 77.9(2) N(1)–Co(1)–N(3) 99.1(2) N(1)–Co(1)–N(4) 100.8(2) N(1)–Co(1)–N(5) 92.3(2) N(1)–Co(1)–N(6) 163.3(2) N(2)–Co(1)–N(3) 98.1(2) N(2)–Co(1)–N(4) 175.1(2) N(2)–Co(1)–N(5) 90.1(2) N(2)–Co(1)–N(6) 88.5(2) N(3)–Co(1)–N(4) 77.4(2) N(3)–Co(1)–N(5) 167.2(2) N(3)–Co(1)–N(6) 92.3(2) N(4)–Co(1)–N(5) 94.6(2) N(4)–Co(1)–N(6) 93.6(2) N(5)–Co(1)–N(6) 77.9(2)
S-15
Table S4. Selected bond lengths (Å) and angles (°) of Compound 2.
Ag(1)–I(1) 2.8707(5) Ag(1)–I(2) 2.8775(5) Ag(1)–I(3) 2.7576(4) Ag(1)–I(3)#1 3.1733(5) Ag(1)–Ag(1)#1 2.9590(7) Ag(2)–I(1) 2.9346(5) Ag(2)–I(2) 2.9371(5) Ag(2)–I(3)#1 3.0317(5) Ag(2)–I(4) 2.7088(4) Ni(1)–N(1) 2.033(3) Ni(1)–N(2) 2.319(3) Ni(1)–N(3) 2.018(3) Ni(1)–N(4) 2.394(3) Ni(1)–N(5) 2.039(3) Ni(1)–N(6) 2.052(3) I(1)–Ag(1)–I(2) 110.212(14) I(1)–Ag(1)–I(3) 121.718(16) I(1)–Ag(1)–I(3)#1 90.820(13) I(2)–Ag(1)–I(3) 113.979(16) I(2)–Ag(1)–Ag(1)#1 117.58(2) I(2)–Ag(1)–I(3)#1 94.510(13) I(3)–Ag(1)–I(3)#1 120.637(13) I(1)–Ag(1)–Ag(1)#1 120.35(2) I(3)–Ag(1)–Ag(1)#1 67.330(13) I(3)#1–Ag(1)–Ag(1)#1 53.307(13) I(1)–Ag(2)–I(2) 106.826(14) I(1)–Ag(2)–I(3)#1 92.476(13) I(1)–Ag(2)–I(4) 116.219(17) I(2)–Ag(2)–I(3)#1 96.343(14) I(2)–Ag(2)–I(4) 122.017(15) I(3)#1–Ag(2)–I(4) 117.620(15) Ag(1)–I(1)–Ag(2) 58.537(12) Ag(1)–I(2)–Ag(2) 58.435(12) Ag(1)–I(3)–Ag(1)#1 59.363(13) Ag(1)–I(3)–Ag(2)#1 113.601(13) Ag(1)#1–I(3)–Ag(2)#1 54.392(10) N(1)–Ni(1)–N(2) 76.46(13) N(1)–Ni(1)–N(3) 94.26(13) N(1)–Ni(1)–N(4) 97.19(13) N(1)–Ni(1)–N(5) 94.27(13) N(1)–Ni(1)–N(6) 168.01(13)
S-16 N(2)–Ni(1)–N(3) 103.47(12) N(2)–Ni(1)–N(4) 173.59(12) N(2)–Ni(1)–N(5) 96.47(12) N(2)–Ni(1)–N(6) 92.64(12) N(3)–Ni(1)–N(4) 75.93(12) N(3)–Ni(1)–N(5) 159.66(13) N(3)–Ni(1)–N(6) 93.11(13) N(4)–Ni(1)–N(5) 84.70(12) N(4)–Ni(1)–N(6) 93.77(12) N(5)–Ni(1)–N(6) 81.87(13)
S-17
Table S5. Selected bond lengths (Å) and angles (°) of Compound 3.
Ag(1A)–I(1) 2.7347(9) Ag(1A)–I(1)#1 3.1384(9) Ag(1A)–I(2) 2.8852(10) Ag(1A)–I(3) 2.8551(9) Ag(1A)–Ag(1B) 2.050(3) Ag(1A)–Ag(1A)#1 2.9670(16) Ag(1A)–Ag(1B)#1 2.117(3) Ag(1A)–Ag(2A)#1 2.872(3) Ag(1A)–Ag(2B)#1 2.550(4) Ag(1B)–I(1) 2.964(3) Ag(1B)–I(1)#1 2.903(3) Ag(1B)–I(2) 3.078(3) Ag(1B)–I(3)#1 3.093(3) Ag(1B)–Ag(1A)#1 2.117(3) Ag(1B)–Ag(1B)#1 2.927(5) Ag(2A)–I(1) 3.103(5) Ag(2A)–I(2)#1 2.965(5) Ag(2A)–I(3)#1 3.028(5) Ag(2A)–I(4A) 2.707(4) Ag(2B)–I(1) 2.885(5) Ag(2B)–I(2)#1 2.845(5) Ag(2B)–I(3)#1 2.895(5) Ag(2B)–I(4A) 3.033(5) Ag(2B)–I(4B) 2.748(6) Zn(1)–N(1) 2.164(6) Zn(1)–N(2) 2.195(6) Zn(1)–N(3) 2.217(5) Zn(1)–N(4) 2.120(6) Zn(1)–N(5) 2.176(5) Zn(1)–N(6) 2.154(6) I(1)–Ag(1A)–I(1)#1 119.78(3) I(1)–Ag(1A)–I(2) 118.19(3) I(1)–Ag(1A)–I(3) 114.79(3) I(1)#1–Ag(1A)–I(2) 92.32(3) I(1)#1–Ag(1A)–I(3) 93.71(3) I(2)–Ag(1A)–I(3) 113.74(3) Ag(1A)#1–Ag(1A)–Ag(1B) 45.53(8) Ag(1A)#1–Ag(1A)–Ag(1B)#1 43.69(7) Ag(1A)#1–Ag(1A)–Ag(2A)#1 115.10(11) Ag(1A)#1–Ag(1A)–Ag(2B)#1 113.02(12) Ag(1A)#1–Ag(1A)–I(1) 66.65(3) Ag(1A)#1–Ag(1A)–I(1)#1 53.13(3)
S-18 Ag(1A)#1–Ag(1A)–I(2) 118.57(4) Ag(1A)#1–Ag(1A)–I(3) 117.06(4) Ag(1B)–Ag(1A)–Ag(1B)#1 89.22(10) Ag(1B)–Ag(1A)–Ag(2A)#1 106.76(14) Ag(1B)#1–Ag(1A)–Ag(2A)#1 108.37(13) Ag(1B)–Ag(1A)–Ag(2B)#1 105.41(14) Ag(1B)#1–Ag(1A)–Ag(2B)#1 106.91(14) Ag(1B)–Ag(1A)–I(1) 75.03(8) Ag(1B)–Ag(1A)–I(1)#1 64.07(8) Ag(1B)#1–Ag(1A)–I(1) 72.22(8) Ag(1B)#1–Ag(1A)–I(1)#1 65.32(8) Ag(1B)–Ag(1A)–I(2) 75.04(8) Ag(1B)#1–Ag(1A)–I(2) 156.92(8) Ag(1B)–Ag(1A)–I(3) 157.02(9) Ag(1B)#1–Ag(1A)–I(3) 75.30(7) Ag(2A)#1–Ag(1A)–Ag(2B)#1 2.1(2) Ag(2A)#1–Ag(1A)–I(1) 178.06(11) Ag(2A)#1–Ag(1A)–I(1)#1 61.97(11) Ag(2A)#1–Ag(1A)–I(2) 61.98(11) Ag(2A)#1–Ag(1A)–I(3) 63.83(11) Ag(2B)#1–Ag(1A)–I(1) 179.04(12) Ag(2B)#1–Ag(1A)–I(1)#1 59.90(11) Ag(2B)#1–Ag(1A)–I(2) 62.77(12) Ag(2B)#1–Ag(1A)–I(3) 64.48(11) I(1)–Ag(1B)–I(1)#1 120.16(9) I(1)–Ag(1B)–I(2) 105.91(8) I(1)#1–Ag(1B)–I(2) 93.24(8) I(1)–Ag(1B)–I(3)#1 92.53(8) I(1)#1–Ag(1B)–I(3)#1 103.48(8) I(2)–Ag(1B)–I(3)#1 144.50(9) Ag(1A)–Ag(1B)–Ag(1A)#1 90.78(10) Ag(1A)–Ag(1B)–Ag(1B)#1 46.33(8) Ag(1A)#1–Ag(1B)–Ag(1B)#1 44.45(8) Ag(1A)–Ag(1B)–I(1) 63.05(7) Ag(1A)–Ag(1B)–I(1)#1 76.50(8) Ag(1A)#1–Ag(1B)–I(1) 74.20(8) Ag(1A)#1–Ag(1B)–I(1)#1 63.79(7) Ag(1A)–Ag(1B)–I(2) 64.91(8) Ag(1A)#1–Ag(1B)–I(2) 150.63(12) Ag(1A)–Ag(1B)–I(3)#1 149.22(12) Ag(1A)#1–Ag(1B)–I(3)#1 63.23(7) Ag(1B)#1–Ag(1B)–I(1) 59.04(9) Ag(1B)#1–Ag(1B)–I(1)#1 61.12(9) Ag(1B)#1–Ag(1B)–I(2) 109.48(13)
S-19 Ag(1B)#1–Ag(1B)–I(3)#1 106.02(13) I(1)–Ag(2A)–I(2)#1 91.53(10) I(1)–Ag(2A)–I(3)#1 91.12(11) I(1)–Ag(2A)–I(4A) 117.4(2) I(2)#1–Ag(2A)–I(3)#1 106.69(12) I(2)#1–Ag(2A)–I(4A) 120.0(2) I(3)#1–Ag(2A)–I(4A) 122.5(2) Ag(1A)#1–Ag(2A)–I(1) 63.23(7) Ag(1A)#1–Ag(2A)–I(2)#1 59.22(7) Ag(1A)#1–Ag(2A)–I(3)#1 57.81(8) Ag(1A)#1–Ag(2A)–I(4A) 179.2(3) I(1)–Ag(2B)–I(2)#1 98.72(13) I(1)–Ag(2B)–I(3)#1 98.45(15) I(1)–Ag(2B)–I(4A) 114.1(2) I(1)–Ag(2B)–I(4B) 115.3(2) I(2)#1–Ag(2B)–I(3)#1 113.76(15) I(2)#1–Ag(2B)–I(4A) 113.4(2) I(2)#1–Ag(2B)–I(4B) 111.7(2) I(3)#1–Ag(2B)–I(4A) 116.11(19) I(3)#1–Ag(2B)–I(4B) 116.86(19) I(4A)–Ag(2B)–I(4B) 1.8(2) Ag(1A)#1–Ag(2B)–I(1) 70.23(11) Ag(1A)#1–Ag(2B)–I(2)#1 64.39(10) Ag(1A)#1–Ag(2B)–I(3)#1 62.88(11) Ag(1A)#1–Ag(2B)–I(4A) 175.6(2) Ag(1A)#1–Ag(2B)–I(4B) 174.1(2) Ag(1A)–I(1)–Ag(1A)#1 60.22(3) Ag(1A)–I(1)–Ag(1B) 41.92(5) Ag(1A)–I(1)–Ag(1B)#1 44.00(6) Ag(1A)#1–I(1)–Ag(1B) 40.48(5) Ag(1A)#1–I(1)–Ag(1B)#1 39.43(5) Ag(1A)–I(1)–Ag(2A) 115.01(7) Ag(1A)#1–I(1)–Ag(2A) 54.80(7) Ag(1A)–I(1)–Ag(2B) 110.09(9) Ag(1A)#1–I(1)–Ag(2B) 49.87(9) Ag(1B)–I(1)–Ag(1B)#1 59.84(9) Ag(1B)–I(1)–Ag(2A) 84.24(10) Ag(1B)#1–I(1)–Ag(2A) 82.97(9) Ag(1B)–I(1)–Ag(2B) 79.95(11) Ag(1B)#1–I(1)–Ag(2B) 78.75(10) Ag(2A)–I(1)–Ag(2B) 4.93(15) Ag(1A)–I(2)–Ag(1B) 40.04(5) Ag(1A)–I(2)–Ag(2A)#1 58.79(8) Ag(1A)–I(2)–Ag(2B)#1 52.84(9)
S-20 Ag(1B)–I(2)–Ag(2A)#1 82.39(9) Ag(1B)–I(2)–Ag(2B)#1 76.51(10) Ag(2A)#1–I(2)–Ag(2B)#1 6.22(14) Ag(1A)–I(3)–Ag(1B)#1 41.46(5) Ag(1A)–I(3)–Ag(2A)#1 58.36(6) Ag(1A)–I(3)–Ag(2B)#1 52.64(8) Ag(1B)#1–I(3)–Ag(2A)#1 83.35(9) Ag(1B)#1–I(3)–Ag(2B)#1 77.67(10) Ag(2A)#1–I(3)–Ag(2B)#1 5.99(12) Ag(2A)–I(4A)–Ag(2B) 1.7(2) N(1)–Zn(1)–N(2) 77.0(2) N(1)–Zn(1)–N(3) 87.6(2) N(1)–Zn(1)–N(4) 160.2(2) N(1)–Zn(1)–N(5) 94.6(2) N(1)–Zn(1)–N(6) 92.9(2) N(2)–Zn(1)–N(3) 91.7(2) N(2)–Zn(1)–N(4) 91.1(2) N(2)–Zn(1)–N(5) 93.4(2) N(2)–Zn(1)–N(6) 165.8(2) N(3)–Zn(1)–N(4) 77.0(2) N(3)–Zn(1)–N(5) 174.8(2) N(3)–Zn(1)–N(6) 97.9(2) N(4)–Zn(1)–N(5) 101.8(2) N(4)–Zn(1)–N(6) 101.3(2) N(5)–Zn(1)–N(6) 77.3(2)
S-21
Table S6. Selected bond lengths (Å) and angles (°) of Compound 4
Ag(1)–I(1) 2.8165(18) Ag(1)–I(2) 2.7441(17) Ag(1)–I(3) 2.6996(18) Ag(2)–I(1) 2.8853(19) Ag(2)–I(2) 2.8470(19) Ag(2)–I(4) 2.8759(11) Ag(3)–I(1) 3.022(2) Ag(3)–I(4) 3.004(2) Ag(3)–I(5) 2.773(2) Ag(3)–I(6) 2.727(3) Ag(3)–Ag(3)#1 3.371(4) Ag(4)–I(4) 2.9491(11) Ag(4)–I(5) 2.7094(16) Ag(4)–I(7) 2.874(2) Ag(4)–Ag(3)#1 3.193(2) Ag(5)–I(4) 3.0774(15) Ag(5)–I(7) 2.946(2) Ag(5)–I(8) 2.6498(19) Co(1)–N(1) 2.132(7) Co(1)–N(2) 2.143(8) Co(1)–N(3) 2.174(7) Co(1)–N(4) 2.102(8) Co(1)–N(5) 2.123(8) Co(1)–N(6) 2.113(7) I(1)–Ag(1)–I(2) 112.40(6) I(1)–Ag(1)–I(3) 123.86(6) I(2)–Ag(1)–I(3) 123.74(7) I(1)–Ag(2)–I(2) 107.43(5) I(1)–Ag(2)–I(4) 108.81(4) I(2)–Ag(2)–I(4) 114.78(4) I(4)–Ag(2)–I(4)#1 101.99(5) I(1)–Ag(3)–I(4) 102.04(6) I(1)–Ag(3)–I(5) 105.55(7) I(1)–Ag(3)–I(6) 114.28(8) I(4)–Ag(3)–I(5) 108.56(7) I(4)–Ag(3)–I(6) 110.80(9) I(5)–Ag(3)–I(6) 114.71(9) I(1)–Ag(3)–Ag(3)#1 56.10(4) I(4)–Ag(3)–Ag(3)#1 100.53(4) I(5)–Ag(3)–Ag(3)#1 52.56(4) I(6)–Ag(3)–Ag(3)#1 148.67(7) I(4)–Ag(4)–I(4)#1 98.54(5)
S-22 I(4)–Ag(4)–I(5) 111.98(4) I(4)–Ag(4)–I(7) 103.78(4) I(5)–Ag(4)–I(7) 123.58(6) I(4)–Ag(4)–Ag(3)#1 106.03(6) I(4)#1–Ag(4)–Ag(3)#1 58.40(4) I(5)–Ag(4)–Ag(3)#1 55.31(5) I(7)–Ag(4)–Ag(3)#1 147.14(4) I(4)–Ag(5)–I(4)#1 93.14(6) I(4)–Ag(5)–I(7) 99.03(4) I(4)–Ag(5)–I(8) 117.21(5) I(7)–Ag(5)–I(8) 125.13(9) Ag(1)–I(1)–Ag(2) 69.31(5) Ag(1)–I(1)–Ag(3) 127.25(5) Ag(2)–I(1)–Ag(3) 71.50(5) Ag(3)–I(1)–Ag(3)#1 67.81(7) Ag(1)–I(2)–Ag(2) 70.87(5) Ag(2)–I(4)–Ag(3) 71.89(6) Ag(2)–I(4)–Ag(4) 73.42(4) Ag(2)–I(4)–Ag(5) 74.88(5) Ag(3)–I(4)–Ag(4) 64.87(5) Ag(3)–I(4)–Ag(5) 117.39(5) Ag(4)–I(4)–Ag(5) 55.42(4) Ag(3)–I(5)–Ag(3)#1 74.87(9) Ag(3)–I(5)–Ag(4) 71.24(5) Ag(4)–I(7)–Ag(5) 57.60(5) N(1)–Co(1)–N(2) 78.1(3) N(1)–Co(1)–N(3) 89.1(3) N(1)–Co(1)–N(4) 165.7(3) N(1)–Co(1)–N(5) 91.6(3) N(1)–Co(1)–N(6) 96.5(3) N(2)–Co(1)–N(3) 91.8(3) N(2)–Co(1)–N(4) 95.0(3) N(2)–Co(1)–N(5) 167.8(3) N(2)–Co(1)–N(6) 96.0(3) N(3)–Co(1)–N(4) 78.5(3) N(3)–Co(1)–N(5) 94.7(3) N(3)–Co(1)–N(6) 171.2(3) N(4)–Co(1)–N(5) 96.4(3) N(4)–Co(1)–N(6) 96.6(3) N(5)–Co(1)–N(6) 78.5(3)
S-23
Table S7. Selected bond lengths (Å) and angles (°) of Compound 5.
Ag(1)–I(1) 2.822(2) Ag(1)–I(2) 2.7402 (19) Ag(1)–I(3) 2.700 (2) Ag(2)–I(1) 2.880 (2) Ag(2)–I(2) 2.853 (2) Ag(2)–I(4) 2.8793 (12) Ag(3)–I(1) 3.031 (3) Ag(3)–I(4) 2.999 (3) Ag(3)–I(5) 2.779 (2) Ag(3)–I(6) 2.735 (3) Ag(4)–I(4) 2.9511 (12) Ag(4)–I(5) 2.7089 (18) Ag(4)–I(7) 2.873 (2) Ag(4)–Ag(3)#1 3.194 (3) Ag(5)–I(4) 3.0740 (16) Ag(5)–I(7) 2.945 (2) Ag(5)–I(8) 2.652 (2) Ni(1)–N(1) 2.107 (8) Ni(1)–N(2) 2.120 (7) Ni(1)–N(3) 2.131 (8) Ni(1)–N(4) 2.153 (8) Ni(1)–N(5) 2.151 (8) Ni(1)–N(6) 2.110 (8) I(1)–Ag(1)–I(2) 112.35 (6) I(1)–Ag(1)–I(3) 123.76 (7) I(2)–Ag(1)–I(3) 123.89 (8) I(1)–Ag(2)–I(2) 107.41 (6) I(1)–Ag(2)–I(4) 108.77 (5) I(2)–Ag(2)–I(4) 114.94 (5) I(4)–Ag(2)–I(4)#1 101.75 (6) I(1)–Ag(3)–I(4) 101.89 (7) I(1)–Ag(3)–I(5) 105.55 (8) I(1)–Ag(3)–I(6) 114.29 (9) I(4)–Ag(3)–I(5) 108.61 (8) I(4)–Ag(3)–I(6) 110.79 (10) I(5)–Ag(3)–I6) 114.78 (10) I(4)–Ag(4)–I(4)#1 98.39 (5) I(4)–Ag(4)–I(5) 112.00 (5) I(4)–Ag(4)–I(7) 103.83 (4) I(5)–Ag(4)–I(7) 123.57 (7) I(4)–Ag(4)–Ag(3)#1 105.97 (7)
S-24 I(4)#1–Ag(4)–Ag(3)#1 58.26 (5) I(5)–Ag(4)–Ag(3)#1 55.45 (5) I(7)–Ag(4)–Ag(3)#1 147.08 (5) I(4)–Ag(5)–I(4)#1 93.21 (6) I(4)–Ag(5)–I(7) 99.21 (5) I(4)–Ag(5)–I(8) 116.99 (6) I(7)–Ag(5)–I(8) 125.18 (9) Ag(1)–I(1)–Ag(2) 69.36 (5) Ag(1)–I(1)–Ag(3) 127.36 (6) Ag(2)–I(1)–Ag(3) 71.57 (6) Ag(3)–I(1)–Ag(3)#1 74.90 (10) Ag(1)–I(2)–Ag(2) 70.89 (6) Ag(2)–I(4)–Ag(3) 72.06 (6) Ag(2)–I(4)–Ag(4) 73.66 (4) Ag(2)–I(4)–Ag(5) 74.96 (5) Ag(3)–I(4)–Ag(4) 64.92 (5) Ag(3)–I(4)–Ag(5) 117.37 (5) Ag(4)–I(4)–Ag(5) 55.32 (4) Ag(3)–I(5)–Ag(3)#1 74.90 (10) Ag(3)–I(5)–Ag(4) 64.92 (5) Ag(4)–I(7)–Ag(5) 57.50 (5) N(1)–Ni(1)–N(2) 78.8 (3) N(1)–Ni(1)–N(3) 91.2 (3) N(1)–Ni(1)–N(4) 166.9 (3) N(1)–Ni(1)–N(5) 93.6 (3) N(1)–Ni(1)–N(6) 97.0 (3) N(2)–Ni(1)–N(3) 96.0 (3) N(2)–Ni(1)–N(4) 95.2 (3) N(2)–Ni(1)–N(5) 170.7 (3) N(2)–Ni(1)–N(6) 97.6 (3) N(3)–Ni(1)–N(4) 77.7 (3) N(3)–Ni(1)–N(5) 89.6 (3) N(3)–Ni(1)–N(6) 165.3 (3) N(4)–Ni(1)–N(5) 93.3 (3) N(4)–Ni(1)–N(6) 95.4 (3) N(5)–Ni(1)–N(6) 77.8 (3)
S-25
Table S8. Selected bond lengths (Å) and angles (°) of Compound 6.
Ag(1)–I(1) 2.8288 (19) Ag(1)–I(2) 2.7425 (18) Ag(1)–I(3) 2.7011 (19) Ag(2)–I(1) 2.881 (2) Ag(2)–I(2) 2.8464 (19) Ag(2)–I(4) 2.8781 (12) Ag(3)–I(1) 3.028 (2) Ag(3)–I(4) 2.983(2) Ag(3)–I(5) 2.785 (2) Ag(3)–I(6) 2.732 (3) Ag(3)–Ag(3)#1 3.352 (4) Ag(4)–I(4) 2.9496 (12) Ag(4)–I(5) 2.7082 (17) Ag(4)–I(7) 2.863 (2) Ag(4)–Ag(3)#1 3.206 (2) Ag(5)–I(4) 3.0837 (16) Ag(5)–I(7) 2.959 (3) Ag(5)–I(8) 2.651 (2) Zn(1)–N(1) 2.079(6) Zn(1)–N(2) 2.094(6) Zn(1)–N(3) 2.090(6) Zn(1)–N(4) 2.072(7) Zn(1)–N(5) 2.100(7) Zn(1)–N(6) 2.065(7) I(1)–Ag(1)–I(2) 111.47(5) I(1)–Ag(1)–I(3) 124.07(6) I(2)–Ag(1)–I(3) 124.46(6) I(1)–Ag(2)–I(2) 107.04(5) I(1)–Ag(2)–I(4) 109.35(4) I(2)–Ag(2)–I(4) 114.33(4) I(4)–Ag(2)–I(4)#1 102.33(5) I(1)–Ag(3)–I(4) 102.81(6) I(1)–Ag(3)–I(5) 106.16(6) I(1)–Ag(3)–I(6) 114.03(7) I(4)–Ag(3)–I(5) 108.14(6) I(4)–Ag(3)–I(6) 111.28(8) I(5)–Ag(3)–I(6) 113.67(8) I(1)–Ag(3)–Ag(3)#1 56.33(3) I(4)–Ag(3)–Ag(3)#1 100.87(4) I(5)–Ag(3)–Ag(3)#1 52.96(4) I(6)–Ag(3)–Ag(3)#1 147.85(6) I(4)–Ag(4)–I(4)#1 98.88(5)
S-26 I(4)–Ag(4)–I(5) 111.32(4) I(4)–Ag(4)–I(7) 104.44(4) I(5)–Ag(4)–I(7) 123.46(6) I(4)–Ag(4)–Ag(3)#1 105.12(6) I(4)#1–Ag(4)–Ag(3)#1 57.73(4) I(5)–Ag(4)–Ag(3)#1 55.42(4) I(7)–Ag(4)–Ag(3)#1 147.50(4) I(4)–Ag(5)–I(4)#1 93.22(6) I(4)–Ag(5)–I(7) 98.92(4) I(4)–Ag(5)–I(8) 117.18(5) I(7)–Ag(5)–I(8) 125.28(9) Ag(1)–I(1)–Ag(2) 69.86(4) Ag(1)–I(1)–Ag(3) 126.94(5) Ag(2)–I(1)–Ag(3) 70.51(5) Ag(3)–I(1)–Ag(3)#1 67.33(6) Ag(1)–I(2)–Ag(2) 71.63(5) Ag(2)–I(4)–Ag(3) 71.22(5) Ag(2)–I(4)–Ag(4) 73.31(4) Ag(2)–I(4)–Ag(5) 74.67(4) Ag(3)–I(4)–Ag(4) 65.50(4) Ag(3)–I(4)–Ag(5) 117.32(4) Ag(4)–I(4)–Ag(5) 54.98(4) Ag(3)–I(5)–Ag(3)#1 74.08(8) Ag(3)–I(5)–Ag(4) 71.48(5) Ag(4)–I(7)–Ag(5) 57.20(5) N(1)–Zn(1)–N(2) 79.9(3) N(1)–Zn(1)–N(3) 91.3(3) N(1)–Zn(1)–N(4) 169.1(3) N(1)–Zn(1)–N(5) 94.1(3) N(1)–Zn(1)–N(6) 95.1(3) N(2)–Zn(1)–N(3) 95.0(2) N(2)–Zn(1)–N(4) 94.8(3) N(2)–Zn(1)–N(5) 172.5(3) N(2)–Zn(1)–N(6) 95.9(2) N(3)–Zn(1)–N(4) 79.7(3) N(3)–Zn(1)–N(5) 89.5(3) N(3)–Zn(1)–N(6) 168.2(3) N(4)–Zn(1)–N(5) 91.9(3) N(4)–Zn(1)–N(6) 94.8(3) N(5)–Zn(1)–N(6) 80.1(3)
S-27
Table S9. Selected bond lengths (Å) and angles (°) of Compound 7.
Ag(1)–I(1) 3.0746 11) Ag(1)–I(2) 2.8426(9) Ag(1)–I(3) 2.8611(10) Ag(1)–I(4) 2.8536(10) Ag(2)–I(1) 2.8790(10) Ag(2)–I(2) 2.8249(10) Ag(2)–I(5) 3.0308(9) Ag(2)–I(6) 2.8337(10) Ag(3)–I(1) 2.8348(9) Ag(3)–I(3) 2.8009(10) Ag(3)–I(5) 2.9933(9) Ag(3)–I(7) 2.8965(9) Ag(4)–I(5) 2.8865(10) Ag(4)–I(7) 2.8255(9) Ag(4)–I(8) 2.8625(10) Ag(4)–I(9) 2.8897(9) Ag(5)–I(5) 2.9125(10) Ag(5)–I(6) 2.7865(9) Ag(5)–I(8) 2.9204(10) Ag(5)–I(10) 2.8094(9) Ag(6)–I(9) 2.9028(11) Ag(6)–I(10) 2.7104(10) Ag(6)–I(11) 2.8432(11) Ag(7)–I(8) 2.9384(11) Ag(7)–I(9) 3.2655(12) Ag(7)–I(11) 2.7957(11) Ag(7)–I(12) 2.6872(10) Ag(8)–I(4)#1 2.7883(10) Ag(8)–I(7) 2.9774(9) Ag(8)–I(9) 2.9862(9) Ag(8)–I(12) 2.8412(11) Co(1)–N(1) 2.190(6) Co(1)–N(2) 2.154(6) Co(1)–N(3) 2.183(6) Co(1)–N(4) 2.126(6) Co(1)–N(5) 2.151(6) Co(1)–N(6) 2.145(6) Co(2)–N(7) 2.179(6) Co(2)–N(8) 2.133(6) Co(2)–N(9) 2.171(6) Co(2)–N(10) 2.160(6) Co(2)–N(11) 2.187(6)
S-28 Co(2)–N(12) 2.131(5) I(1)–Ag(1)–I(2) 99.47(3) I(1)–Ag(1)–I(3) 103.08(3) I(1)–Ag(1)–I(4) 119.35(3) I(2)–Ag(1)–I(3) 117.74(3) I(2)–Ag(1)–I(4) 104.53(3) I(3)–Ag(1)–I(4) 112.67(3) I(1)–Ag(2)–I(2) 104.75(3) I(1)–Ag(2)–I(5) 107.46(3) I(1)–Ag(2)–I(6) 123.69(3) I(2)–Ag(2)–I(5) 105.85(3) I(2)–Ag(2)–I(6) 110.92(3) I(5)–Ag(2)–I(6) 102.96(3) I(1)–Ag(3)–I(3) 111.19(3) I(1)–Ag(3)–I(5) 109.69(3) I(1)–Ag(3)–I(7) 110.73(3) I(3)–Ag(3)–I(5) 98.08(3) I(3)–Ag(3)–I(7) 117.48(3) I(5)–Ag(3)–I(7) 108.79(3) I(5)–Ag(4)–I(7) 113.94(3) I(5)–Ag(4)–I(8) 105.56(3) I(5)–Ag(4)–I(9) 105.05(3) I(7)–Ag(4)–I(8) 115.65(3) I(7)–Ag(4)–I(9) 106.64(3) I(8)–Ag(4)–I(9) 109.49(3) I(5)–Ag(5)–I(6) 107.27(3) I(5)–Ag(5)–I(8) 103.41(3) I(5)–Ag(5)–I(10) 106.13(3) I(6)–Ag(5)–I(8) 105.92(3) I(6)–Ag(5)–I(10) 120.90(3) I(8)–Ag(5)–I(10) 111.80(3) I(9)–Ag(6)–I(10) 125.87(4) I(9)–Ag(6)–I(11) 102.30(3) I(10)–Ag(6)–I(11) 122.69(4) I(8)–Ag(7)–I(9) 98.29(3) I(8)–Ag(7)–I(11) 106.45(3) I(8)–Ag(7)–I(12) 111.47(4) I(9)–Ag(7)–I(11) 94.86(3) I(9)–Ag(7)–I(12) 109.01(4) I(11)–Ag(7)–I(12) 130.87(4) I(4)#1–Ag(8)–I(7) 113.00(3) I(4)#1–Ag(8)–I(9) 104.15(3) I(4)#1–Ag(8)–I(12) 118.30(3)
S-29 I(7)–Ag(8)–I(9) 100.45(3) I(7)–Ag(8)–I(12) 106.65(3) I(9)–Ag(8)–I(12) 112.93(3) Ag(1)–I(1)–Ag(2) 69.75(2) Ag(1)–I(1)–Ag(3) 68.17(2) Ag(2)–I(1)–Ag(3) 72.09(3) Ag(1)–I(2)–Ag(2) 73.94(3) Ag(1)–I(3)–Ag(3) 71.74(3) Ag(1)–I(4)–Ag(8)#2 129.37(4) Ag(2)–I(5)–Ag(3) 67.86(2) Ag(2)–I(5)–Ag(4) 99.07(3) Ag(2)–I(5)–Ag(5) 68.49(2) Ag(3)–I(5)–Ag(4) 63.58(2) Ag(3)–I(5)–Ag(5) 109.85(3) Ag(4)–I(5)–Ag(5) 72.58(3) Ag(2)–I(6)–Ag(5) 73.07(3) Ag(3)–I(7)–Ag(4) 65.57(2) Ag(3)–I(7)–Ag(8) 134.07(3) Ag(4)–I(7)–Ag(8) 70.09(2) Ag(4)–I(8)–Ag(5) 72.81(3) Ag(4)–I(8)–Ag(7) 72.07(3) Ag(5)–I(8)–Ag(7) 115.36(3) Ag(4)–I(9)–Ag(6) 72.47(3) Ag(4)–I(9)–Ag(7) 67.03(3) Ag(4)–I(9)–Ag(8) 69.13(2) Ag(6)–I(9)–Ag(7) 54.68(2) Ag(6)–I(9)–Ag(8) 115.20(3) Ag(7)–I(9)–Ag(8) 62.88(2) Ag(5)–I(10)–Ag(6) 72.10(3) Ag(6)–I(11)–Ag(7) 60.74(3) Ag(7)–I(12)–Ag(8) 72.46(3) N(1)–Co(1)–N(2) 77.2(2) N(1)–Co(1)–N(3) 94.9(2) N(1)–Co(1)–N(4) 93.3(2) N(1)–Co(1)–N(5) 167.4(2) N(1)–Co(1)–N(6) 94.3(2) N(2)–Co(1)–N(3) 89.4(2) N(2)–Co(1)–N(4) 163.4(2) N(2)–Co(1)–N(5) 93.7(2) N(2)–Co(1)–N(6) 96.7(2) N(3)–Co(1)–N(4) 77.8(2) N(3)–Co(1)–N(5) 93.7(2) N(3)–Co(1)–N(6) 169.9(2) N(4)–Co(1)–N(5) 97.5(2)
S-30 N(4)–Co(1)–N(6) 97.6(2) N(5)–Co(1)–N(6) 77.9(2) N(7)–Co(2)–N(8) 77.6(2) N(7)–Co(2)–N(9) 168.3(2) N(7)–Co(2)–N(10) 92.3(2) N(7)–Co(2)–N(11) 92.3(2) N(7)–Co(2)–N(12) 98.0(2) N(8)–Co(2)–N(9) 97.3(2) N(8)–Co(2)–N(10) 97.1(2) N(8)–Co(2)–N(11) 168.4(2) N(8)–Co(2)–N(12) 98.3(2) N(9)–Co(2)–N(10) 77.7(2) N(9)–Co(2)–N(11) 93.6(2) N(9)–Co(2)–N(12) 93.2(2) N(10)–Co(2)–N(11) 88.9(2) N(10)–Co(2)–N(12) 163.0(2) N(11)–Co(2)–N(12) 77.3(2)
Symmetry transformations used to generate equivalent atoms: #1 x, –y+1/2, z+1/2; #2 x, –y+1/2, z– 1/2.
S-31
Table S10. Selected bond lengths (Å) and angles (°) of Compound 8.
Ag(1)–I(1) 3.0662(10) Ag(1)–I(2) 2.8531(11) Ag(1)–I(3) 2.8383(10) Ag(1)–I(4) 2.8501(11) Ag(2)–I(1) 2.8286(10) Ag(2)–I(2) 2.7903(9) Ag(2)–I(5) 2.9892(11) Ag(2)–I(6) 2.8841(10) Ag(3)–I(1) 2.8685(11) Ag(3)–I(3) 2.8150(10) Ag(3)–I(5) 3.0220(11) Ag(3)–I(7) 2.8225(11) Ag(4)–I(5) 2.9054(10) Ag(4)–I(7) 2.7799(11) Ag(4)–I(8) 2.9149(10) Ag(4)–I(9) 2.8023(11) Ag(5)–I(5) 2.8798(10) Ag(5)–I(6) 2.8180(10) Ag(5)–I(8) 2.8505(10) Ag(5)–I(10) 2.8784(11) Ag(6)–I(4)#1 2.7799(11) Ag(6)–I(6) 2.9734(11) Ag(6)–I(10) 2.9738(10) Ag(6)–I(11) 2.8316(10) Ag(7)–I(8) 2.9276(12) Ag(7)–I(10) 3.2412(11) Ag(7)–I(11) 2.6848(11) Ag(7)–I(12) 2.7904(12) Ag(8)–I(9) 2.7009(10) Ag(8)–I(10) 2.8874(11) Ag(8)–I(12) 2.8277(10) Ni(1)–N(1) 2.072(6) Ni(1)–N(2) 2.098(6) Ni(1)–N(3) 2.077(6) Ni(1)–N(4) 2.079(6) Ni(1)–N(5) 2.070(6) Ni(1)–N(6) 2.101(6) Ni(2)–N(7) 2.093(6) Ni(2)–N(8) 2.082(6) Ni(2)–N(9) 2.086(6) Ni(2)–N(10) 2.094(6) Ni(2)–N(11) 2.101(6)
S-32 Ni(2)–N(12) 2.078(6) I(1)–Ag(1)–I(2) 102.59(3) I(1)–Ag(1)–I(3) 99.66(3) I(1)–Ag(1)–I(4) 119.47(4) I(2)–Ag(1)–I(3) 118.83(4) I(2)–Ag(1)–I(4) 112.88(4) I(3)–Ag(1)–I(4) 103.54(3) I(1)–Ag(2)–I(2) 110.66(3) I(1)–Ag(2)–I(5) 109.11(3) I(1)–Ag(2)–I(6) 111.37(3) I(2)–Ag(2)–I(5) 98.35(3) I(2)–Ag(2)–I(6) 117.21(4) I(5)–Ag(2)–I(6) 109.19(3) I(1)–Ag(3)–I(3) 105.16(3) I(1)–Ag(3)–I(5) 107.15(3) I(1)–Ag(3)–I(7) 123.22(3) I(3)–Ag(3)–I(5) 105.73(3) I(3)–Ag(3)–I(7) 111.43(3) I(5)–Ag(3)–I(7) 102.89(3) I(5)–Ag(4)–I(7) 107.05(3) I(5)–Ag(4)–I(8) 103.89(3) I(5)–Ag(4)–I(9) 106.33(3) I(7)–Ag(4)–I(8) 105.99(3) I(7)–Ag(4)–I(9) 120.52(4) I(8)–Ag(4)–I(9) 111.79(3) I(5)–Ag(5)–I(6) 114.32(3) I(5)–Ag(5)–I(8) 106.22(3) I(5)–Ag(5)–I(10) 105.07(3) I(6)–Ag(5)–I(8) 115.46(3) I(6)–Ag(5)–I(10) 106.19(3) I(8)–Ag(5)–I(10) 109.04(3) I(4)#1–Ag(6)–I(6) 114.13(4) I(4)#1–Ag(6)–I(10) 104.01(4) I(4)#1–Ag(6)–I(11) 118.33(4) I(6)–Ag(6)–I(10) 99.98(3) I(6)–Ag(6)–I(11) 106.16(3) I(10)–Ag(6)–I(11) 112.83(3) I(8)–Ag(7)–I(10) 98.14(3) I(8)–Ag(7)–I(11) 111.69(4) I(8)–Ag(7)–I(12) 106.39(4) I(10)–Ag(7)–I(11) 109.06(4) I(10)–Ag(7)–I(12) 95.29(3) I(11)–Ag(7)–I(12) 130.47(4)
S-33 I(9)–Ag(8)–I(10) 125.43(4) I(9)–Ag(8)–I(12) 123.47(4) I(10)–Ag(8)–I(12) 102.83(3) Ag(1)–I(1)–Ag(2) 68.45(3) Ag(1)–I(1)–Ag(3) 69.52(3) Ag(2)–I(1)–Ag(3) 72.65(3) Ag(1)–I(2)–Ag(2) 72.09(3) Ag(1)–I(3)–Ag(3) 73.63(3) Ag(1)–I(4)–Ag(6)#2 129.69(4) Ag(2)–I(5)–Ag(3) 68.31(3) Ag(2)–I(5)–Ag(4) 109.38(3) Ag(2)–I(5)–Ag(5) 63.03(3) Ag(3)–I(5)–Ag(4) 68.62(3) Ag(3)–I(5)–Ag(5) 99.06(3) Ag(4)–I(5)–Ag(5) 72.00(3) Ag(2)–I(6)–Ag(5) 65.12(3) Ag(2)–I(6)–Ag(6) 134.19(3) Ag(5)–I(6)–Ag(6) 70.75(3) Ag(3)–I(7)–Ag(4) 73.25(3) Ag(4)–I(8)–Ag(5) 72.28(3) Ag(4)–I(8)–Ag(7) 115.16(3) Ag(5)–I(8)–Ag(7) 72.35(3) Ag(4)–I(9)–Ag(8) 72.52(3) Ag(5)–I(10)–Ag(6) 69.94(3) Ag(5)–I(10)–Ag(7) 67.45(3) Ag(5)–I(10)–Ag(8) 73.29(3) Ag(6)–I(10)–Ag(7) 63.14(2) Ag(6)–I(10)–Ag(8) 116.05(3) Ag(7)–I(10)–Ag(8) 54.97(3) Ag(6)–I(11)–Ag(7) 72.44(3) Ag(7)–I(12)–Ag(8) 60.86(3) N(1)–Ni(1)–N(2) 79.9(2) N(1)–Ni(1)–N(3) 94.2(2) N(1)–Ni(1)–N(4) 96.1(2) N(1)–Ni(1)–N(5) 167.9(2) N(1)–Ni(1)–N(6) 93.4(2) N(2)–Ni(1)–N(3) 93.1(2) N(2)–Ni(1)–N(4) 171.9(2) N(2)–Ni(1)–N(5) 90.5(2) N(2)–Ni(1)–N(6) 93.3(2) N(3)–Ni(1)–N(4) 80.2(2) N(3)–Ni(1)–N(5) 93.5(2) N(3)–Ni(1)–N(6) 170.8(2) N(4)–Ni(1)–N(5) 94.4(2)
S-34 N(4)–Ni(1)–N(6) 93.9(2) N(5)–Ni(1)–N(6) 79.8(2) N(7)–Ni(2)–N(8) 79.0(2) N(7)–Ni(2)–N(9) 90.3(2) N(7)–Ni(2)–N(10) 92.3(2) N(7)–Ni(2)–N(11) 92.5(2) N(7)–Ni(2)–N(12) 170.8(2) N(8)–Ni(2)–N(9) 167.3(2) N(8)–Ni(2)–N(10) 93.7(2) N(8)–Ni(2)–N(11) 94.2(2) N(8)–Ni(2)–N(12) 96.8(2) N(9)–Ni(2)–N(10) 79.8(2) N(9)–Ni(2)–N(11) 93.0(2) N(9)–Ni(2)–N(12) 94.7(2) N(10)–Ni(2)–N(11) 171.4(2) N(10)–Ni(2)–N(12) 96.2(2) N(11)–Ni(2)–N(12) 79.6(2)
Symmetry transformations used to generate equivalent atoms: #1 x, –y+3/2, z–1/2; #2 x, –y+3/2, z+1/2.
S-35
Table S11. Selected bond lengths (Å) and angles (°) of Compound 9.
Ag(1)–I(1) 3.0701(11) Ag(1)–I(2) 2.8604(10) Ag(1)–I(3) 2.8429(10) Ag(1)–I(4) 2.8551(11) Ag(2)–I(1) 2.8265(9) Ag(2)–I(2) 2.7944(10) Ag(2)–I(5) 2.9935(10) Ag(2)–I(6) 2.8897(10) Ag(3)–I(1) 2.8695(10) Ag(3)–I(3) 2.8209(10) Ag(3)–I(5) 3.0311(10) Ag(3)–I(7) 2.8264(11) Ag(4)–I(5) 2.9066(10) Ag(4)–I(7) 2.7812(10) Ag(4)–I(8) 2.9137(10) Ag(4)–I(9) 2.8060(10) Ag(5)–I(5) 2.8830(10) Ag(5)–I(6) 2.8212(10) Ag(5)–I(8) 2.8527(10) Ag(5)–I(10) 2.8781(10) Ag(6)–I(4)#1 2.7802(11) Ag(6)–I(6) 2.9854(10) Ag(6)–I(10) 2.9698(10) Ag(6)–I(11) 2.8438(11) Ag(7)–I(9) 2.7044(10) Ag(7)–I(10) 2.8893(11) Ag(7)–I(12) 2.8357(10) Ag(8)–I(8) 2.9301(12) Ag(8)–I(10) 3.2377(12) Ag(8)–I(11) 2.6821(10) Ag(8)–I(12) 2.8005(11) Zn(1)–N(1) 2.075(6) Zn(1)–N(2) 2.093(6) Zn(1)–N(3) 2.088(5) Zn(1)–N(4) 2.082(6) Zn(1)–N(5) 2.100(6) Zn(1)–N(6) 2.081(6) Zn(2)–N(7) 2.085(6) Zn(2)–N(8) 2.099(5) Zn(2)–N(9) 2.091(6) Zn(2)–N(10) 2.088(6) Zn(2)–N(11) 2.081(5)
S-36 Zn(2)–N(12) 2.093(6) I(1)–Ag(1)–I(2) 102.53(3) I(1)–Ag(1)–I(3) 99.49(3) I(1)–Ag(1)–I(4) 119.75(4) I(2)–Ag(1)–I(3) 118.75(3) I(2)–Ag(1)–I(4) 112.85(4) I(3)–Ag(1)–I(4) 103.59(3) I(1)–Ag(2)–I(2) 110.85(3) I(1)–Ag(2)–I(5) 108.94(3) I(1)–Ag(2)–I(6) 111.52(3) I(2)–Ag(2)–I(5) 98.48(3) I(2)–Ag(2)–I(6) 116.99(3) I(5)–Ag(2)–I(6) 109.08(3) I(1)–Ag(3)–I(3) 105.01(3) I(1)–Ag(3)–I(5) 106.78(3) I(1)–Ag(3)–I(7) 123.52(4) I(3)–Ag(3)–I(5) 105.45(3) I(3)–Ag(3)–I(7) 111.77(3) I(5)–Ag(3)–I(7) 102.93(3) I(5)–Ag(4)–I(7) 107.36(3) I(5)–Ag(4)–I(8) 103.72(3) I(5)–Ag(4)–I(9) 106.39(3) I(7)–Ag(4)–I(8) 106.02(3) I(7)–Ag(4)–I(9) 120.22(4) I(8)–Ag(4)–I(9) 111.86(3) I(5)–Ag(5)–I(6) 114.31(3) I(5)–Ag(5)–I(8) 105.90(3) I(5)–Ag(5)–I(10) 105.32(3) I(6)–Ag(5)–I(8) 115.46(3) I(6)–Ag(5)–I(10) 106.33(3) I(8)–Ag(5)–I(10) 109.01(3) I(4)#1–Ag(6)–I(6) 114.11(4) I(4)#1–Ag(6)–I(10) 104.42(3) I(4)#1–Ag(6)–I(11) 118.58(4) I(6)–Ag(6)–I(10) 99.99(3) I(6)–Ag(6)–I(11) 105.78(3) I(10)–Ag(6)–I(11) 112.52(3) I(9)–Ag(7)–I(10) 125.57(4) I(9)–Ag(7)–I(12) 122.98(4) I(10)–Ag(7)–I(12) 102.66(3) I(8)–Ag(8)–I(10) 98.18(3) I(8)–Ag(8)–I(11) 111.87(4) I(8)–Ag(8)–I(12) 106.19(3)
S-37 I(10)–Ag(8)–I(11) 109.15(4) I(10)–Ag(8)–I(12) 95.23(3) I(11)–Ag(8)–I(12) 130.43(4) Ag(1)–I(1)–Ag(2) 68.49(3) Ag(1)–I(1)–Ag(3) 69.87(3) Ag(2)–I(1)–Ag(3) 73.03(3) Ag(1)–I(2)–Ag(2) 72.00(3) Ag(1)–I(3)–Ag(3) 73.91(3) Ag(1)–I(4)–Ag(6)#2 129.56(4) Ag(2)–I(5)–Ag(3) 68.47(2) Ag(2)–I(5)–Ag(4) 109.44(3) Ag(2)–I(5)–Ag(5) 63.11(2) Ag(3)–I(5)–Ag(4) 68.41(2) Ag(3)–I(5)–Ag(5) 99.21(3) Ag(4)–I(5)–Ag(5) 72.17(3) Ag(2)–I(6)–Ag(5) 65.18(3) Ag(2)–I(6)–Ag(6) 134.19(3) Ag(5)–I(6)–Ag(6) 70.68(3) Ag(3)–I(7)–Ag(4) 73.10(3) Ag(4)–I(8)–Ag(5) 72.50(3) Ag(4)–I(8)–Ag(8) 115.25(3) Ag(5)–I(8)–Ag(8) 72.23(3) Ag(4)–I(9)–Ag(7) 72.13(3) Ag(5)–I(10)–Ag(6) 70.15(3) Ag(5)–I(10)–Ag(7) 73.03(3) Ag(5)–I(10)–Ag(8) 67.46(3) Ag(6)–I(10)–Ag(7) 116.25(3) Ag(6)–I(10)–Ag(8) 63.37(2) Ag(7)–I(10)–Ag(8) 54.99(2) Ag(6)–I(11)–Ag(8) 72.45(3) Ag(7)–I(12)–Ag(8) 60.64(3) N(1)–Zn(1)–N(2) 79.5(2) N(1)–Zn(1)–N(3) 94.7(2) N(1)–Zn(1)–N(4) 93.8(2) N(1)–Zn(1)–N(5) 90.1(2) N(1)–Zn(1)–N(6) 167.6(2) N(2)–Zn(1)–N(3) 94.6(2) N(2)–Zn(1)–N(4) 170.9(2) N(2)–Zn(1)–N(5) 93.2(2) N(2)–Zn(1)–N(6) 93.7(2) N(3)–Zn(1)–N(4) 79.8(2) N(3)–Zn(1)–N(5) 171.5(2) N(3)–Zn(1)–N(6) 96.3(2) N(4)–Zn(1)–N(5) 92.9(2)
S-38 N(4)–Zn(1)–N(6) 94.0(2) N(5)–Zn(1)–N(6) 79.9(2) N(7)–Zn(2)–N(8) 79.6(2) N(7)–Zn(2)–N(9) 93.7(2) N(7)–Zn(2)–N(10) 167.3(2) N(7)–Zn(2)–N(11) 96.6(2) N(7)–Zn(2)–N(12) 94.4(2) N(8)–Zn(2)–N(9) 92.3(2) N(8)–Zn(2)–N(10) 90.0(2) N(8)–Zn(2)–N(11) 170.9(2) N(8)–Zn(2)–N(12) 92.2(2) N(9)–Zn(2)–N(10) 79.3(2) N(9)–Zn(2)–N(11) 96.2(2) N(9)–Zn(2)–N(12) 171.3(2) N(10)–Zn(2)–N(11) 94.7(2) N(10)–Zn(2)–N(12) 93.3(2) N(11)–Zn(2)–N(12) 79.7(2)
Symmetry transformations used to generate equivalent atoms: #1 x, –y+3/2, z–1/2; #2 x, –y+3/2, z+1/2.
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Table S12. Hydrogen bond lengths (Å) and angles (°) for Compounds 1–9.
Compound 1
D–H···A d(H···A) d(D···A) <(DHA)
C(1)–H(1)···O(1)#8 2.25 3.146(9) 156.0 C(2)–H(2)···I(1)#2 3.33 4.021(8) 131.5 C(9)–H(9)···I(4A)#7 3.06 3.806(9) 136.1 C(9)–H(9)···I(4B)#7 3.05 3.824(9) 140.2 C(10)–H(10)···N(6) 2.63 3.166(9) 116.0 C(13)–H(13)···O(3)#6 2.23 3.092(11) 150.9 C(14)–H(14)···I(1)#5 3.16 3.873(9) 133.1 C(21)–H(21)···I(1)#1 3.23 3.867(7) 126.2 C(22)–H(22)···O(2) 2.25 3.030(10) 138.2 C(26)–H(26)···I(4A)#4 3.23 4.000(9) 139.7 C(26)–H(26)···I(4B)#4 3.23 3.971(9) 135.7 C(39)–H(39A)···O(3)#3 2.59 3.450(14) 146.2 C(42)–H(42B)···I(2A) 3.21 4.031(13) 142.8 C(44)–H(44A)···I(1)#1 3.16 3.835(10) 127.4 C(45)–H(45A)···I(4A)#2 3.03 3.792(13) 135.7 C(45)–H(45A)···I(4B)#2 3.21 3.947(13) 133.6
Symmetry transformations used to generate equivalent atoms: #1 –x+2, –y+1, –z+1; #2 x, y, z+1; #3 –x+1, –y+1, –z+2; #4 –x+1, –y+1, –z+1; #5 –x+2, –y, –z+1; #6 x, y–1, z; #7 –x+1, –y,–z+1; #8 x+1, y, z.
S-40 Compound 2
D–H···A d(H···A) d(D···A) <(DHA)
C(1)–H(1)···N(4) 2.66 3.316(5) 126.4 C(1)–H(1)···O(2) 2.24 3.020(6) 139.2 C(2)–H(2)···I(3)#4 3.08 3.790(5) 132.8 C(9)–H(9)···I(3)#8 3.16 3.890(4) 134.6 C(10)–H(10)···O(3)#7 2.34 3.158(6) 143.5 C(13)–H(13)···O(1)#6 2.22 3.035(6) 143.4 C(21)–H(21)···I(4)#5 3.18 3.949(4) 138.8 C(25)–H(25)···I(1)#4 3.23 3.965(4) 135.9 C(26)–H(26)···O(3)#3 2.65 3.217(5) 118.5 C(39)–H(39C)···O(2) 2.49 3.322(6) 142.9 C(42)–H(42B)···I(4)#2 3.17 4.034(5) 147.4
Symmetry transformations used to generate equivalent atoms: #1 –x+2, –y+2, –z+2; #2 x, y–1, z; #3 –x+1, –y, –z; #4 x, y–1, z–1; #5 –x+1, –y+1, –z+1; #6 –x+2, –y+1, –z+1; #7 x, y+1, z; #8 x, y, z–1.
Compound 3
D–H···A d(H···A) d(D···A) <(DHA)
C(13)–H(13)···N(1) 2.67 3.200(9) 115.6
C(22)–H(22)···O(1)#2 2.24 3.143(9) 158.2
C(25)–H(25)···O(2)#3 2.28 3.053(10) 137.5
S-41
C(45)–H(45B)···O(1) 2.52 3.244(18) 130.8
C(38)–H(38A)···O(3) 2.58 3.385(14) 139.8
O(4)–H(4B)···O(1)#4 2.19 3.00(2) 164.9
Symmetry transformations used to generate equivalent atoms: #1 –x, –y, –z; #2 x+1, y, z; #3 x, y+1, z; #4 –x+1, –y+1, –z+1.
Compound 4
D–H···A d(H···A) d(D···A) <(DHA)
C(1)–H(1)···N(5) 2.65 3.196(12) 117.5 C(2)–H(2)···I(7)#4 3.27 3.898(10) 126.1 C(13)–H(13)···N(1) 2.65 3.197(12) 117.7 C(14)–H(14)···I(2)#4 3.24 3.962(11) 135.0 C(14)–H(14)···I(4)#4 3.26 3.923(13) 129.1 C(21)–H(21)···I(1)#3 3.34 4.009(10) 129.6 C(26)–H(26)···I(5) 3.28 3.896(13) 125.4 C(33)–H(33)···I(5)#2 3.23 3.985(10) 138.3
Symmetry transformations used to generate equivalent atoms: #1 x, –y+1/2, z; #2 –x+1, –y+1, – z; #3 –x+1, –y+1, –z+1; #4 x+1, y, z.
Compound 5
D–H···A d(H···A) d(D···A) <(DHA)
C(1)–H(1)···N(5) 2.62 3.128(16) 113.9
C(2)–H(2)···I(7)#2 3.23 3.868(12) 126.2
S-42 C(14)–H(14)···I(2)#2 3.23 3.963(14) 135.0 C(14)–H(14)···I(4)#2 3.22 3.887(18) 128.8 C(21)–H(21)···I(1)#3 3.31 3.993(14) 130.1 C(26)–H(26)···I(5) 3.13 3.763(15) 125.9 C(33)–H(33)···I(5)#4 3.16 3.933(12) 139.7
Symmetry transformations used to generate equivalent atoms: #1 x, –y+1/2, z; #2 x+1, y, z; #3 – x+1, –y+1, –z+1; #4 –x+1, –y+1, –z.
Compound 6
D–H···A d(H···A) d(D···A) <(DHA)
C(2)–H(2)···I(5)#2 3.19 3.839(11) 128.2 C(9)–H(9)···I(5) 3.21 3.967(8) 138.9 C(13)–H(13)···N(1) 2.61 3.134(11) 115.6 C(14)–H(14)···I(7)#3 3.25 3.881(9) 126.7 C(25)–H(25)···N(3) 2.62 3.139(11) 115.6 C(26)–H(26)···I(2)#3 3.22 3.957(10) 137.0 C(26)–H(26)···I(4)#3 3.30 3.946(13) 127.7
Symmetry transformations used to generate equivalent atoms: #1 x, –y+1/2, z; #2 –x+1, –y+1, – z+1; #3 –x+2, –y+1, –z+1.
Compound 7
D–H···A d(H···A) d(D···A) <(DHA)
C(14)–H(14)···I(1)#6 3.23 3.984(9) 138.1
S-43 C(22)–H(22)···O(4) 2.34 3.119(13) 140.0 C(33)–H(33)···I(11)#3 3.23 4.009(9) 141.3 C(45)–H(45)···I(2)#4 3.18 3.982(8) 144.1 C(46)–H(46)···I(3)#4 3.23 3.982(8) 138.6 C(50)–H(50)···O(2)#7 2.59 3.11(2) 114.6 C(61)–H(61)···N(10) 2.67 3.214(9) 117.4 C(62)–H(62)···I(9)#6 3.02 3.811(8) 142.7 C(69)–H(69)···I(7)#5 3.29 4.012(8) 135.3 C(70)–H(70)···I(4)#4 3.25 3.919(8) 129.4 C(83)–H(83A)···I(9)#3 3.09 3.947(14) 148.0 C(83)–H(83B)···I(3)#2 3.28 4.078(13) 141.0
Symmetry transformations used to generate equivalent atoms: #1 x, –y+1/2, z+1/2; #2 x, –y+1/2, z–1/2; #3 x, y, z–1; #4 x+1, y, z; #5 x+1, –y+1/2, z–1/2; #6 –x+1, y–1/2, –z+3/2; #7 –x+2, –y, – z+1.
Compound 8
D–H···A d(H···A) d(D···A) <(DHA)
C(1)–H(1)···O(4)#3 2.32 3.086(12) 138.2 C(9)–H(9)···I(1)#4 3.22 3.966(8) 137.9 C(10)–H(10)···N(5) 2.61 3.134(10) 115.5 C(21)–H(21)···I(12)#3 3.26 3.993(8) 136.5 C(22)–H(22)···I(11)#3 3.31 4.096(8) 142.1 C(26)–H(26)···I(9)#4 3.33 4.070(8) 137.8
S-44 C(37)–H(37)···N(9) 2.61 3.144(10) 116.4 C(38)–H(38)···I(10)#5 3.01 3.792(8) 141.2 C(45)–H(45)···I(6)#6 3.32 4.019(8) 133.1 C(46)–H(46)···I(4)#7 3.25 3.880(8) 125.9 C(57)–H(57)···O(1)#6 2.55 3.10(2) 117.6 C(61)–H(61)···N(7) 2.67 3.202(10) 116.5 C(69)–H(69)···I(3)#7 3.23 3.978(8) 137.9 C(70)–H(70)···I(2)#7 3.17 3.924(8) 138.6 C(74)–H(74C)···I(12) 3.24 4.015(16) 138.1 C(83)–H(83B)···I(2)#1 3.10 4.065(13) 176.0 C(83)–H(83C)···I(10) 3.10 3.962(14) 148.5
Symmetry codes: #1 x, –y+3/2, z–1/2; #2 x, –y+3/2, z+1/2; #3 x+1, y, z; #4 –x+1, y+1/2, –z+1/2; #5 x, –y+1/2, z–1/2; #6 –x+1, y–1/2, –z+1/2; #7 –x+1, –y+1, –z+1.
Compound 9
D–H···A d(H···A) d(D···A) <(DHA)
C(13)–H(13)···I(11)#3 3.33 4.101(8) 141.2 C(14)–H(14)···I(12)#3 3.27 3.996(8) 135.9 C(22)–H(22)···N(5) 2.69 3.221(10) 116.6 C(25)–H(25)···N(1) 2.62 3.141(10) 115.4 C(26)–H(26)···I(1) 3.21 3.961(8) 137.8 C(34)–H(34)···O(3)#3 2.35 3.119(12) 139.1 C(37)–H(37)···I(4) 3.23 3.870(7) 127.2
S-45 C(45)–H(45)···I(10)#4 3.02 3.797(8) 141.2 C(46)–H(46)···N(10) 2.61 3.137(9) 115.9 C(61)–H(61)···I(2) 3.19 3.937(8) 138.1 C(62)–H(62)···I(3) 3.23 3.978(8) 138.1 C(70)–H(70)···N(8) 2.65 3.192(9) 117.0 C(80)–H(80A)···I(2)#1 3.11 4.058(14) 167.7 C(80)–H(80B)···I(10) 3.08 3.977(15) 153.9 C(84)–H(84C)···I(2)#1 3.29 4.193(17) 154.9
Symmetry transformations used to generate equivalent atoms: #1 x, –y+3/2, z–1/2; #2 x, –y+3/2, z+1/2; #3 –x, y–1/2, –z+1/2; #4 –x+1, y+1/2, –z+3/2.
S-46
Figure S1. Experimental and simulated powder XRD patterns of compounds 1 (a), 2 (b) and 3 (c)
S-47
Figure S2. Experimental and simulated powder XRD patterns of compounds 4 (a), 5 (b) and 6 (c)
S-48
Figure S3. Experimental and simulated powder XRD patterns of compounds 7 (a), 8 (b) and 9 (c)
S-49
Figure S4. IR spectra of compounds 1–3.
S-50
Figure S6. IR spectra of compounds 7–9.
S-51
Figure S8. Time-dependent PXRD patterns of compound 1 with crystallization time from 5 days
to 30 days.
S-52
Figure S10. Optical diffuse reflectance spectra of compounds 1–9.
Figure S11. Absorption spectra of CV solution in the presence of compounds 1 (a), 2 (b) and 3 (c)
under visible light.
Figure S12. Absorption spectra of CV solution in the presence of compounds 4 (a), 5 (b) and 6 (c)
S-53
Figure S13. Absorption spectra of CV solution in the presence of compounds 7 (a), 8 (b) and 9 (c)
under visible light.
Figure S14. Absorption spectra of RhB solution in the presence of compounds 1 (a), 2 (b) and 3 (c)
S-54
Figure S15. Absorption spectra of RhB solution in the presence of compounds 4 (a), 5 (b) and 6 (c)
under visible light.
Figure S16. Absorption spectra of RhB solution in the presence of compounds 7 (a), 8 (b) and 9 (c)
S-55
Figure S17. Visible light-driven photocatalytic degradations of RhB using compounds 1–9 (a, c and
e), and the calculated degradation rate of RhB using compounds 1–9 (b, d and f).
S-56
Figure S18. The radical-trapping experiments using compound 3 for the degradation of CV.
S-57
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