[Ag-Ag] 2+ Unit-Encapsulated Trimetallic Cages: One-pot Syntheses and Modulation of Argentophilic Interactions by the Uncoordinated Substituents

[Ag-Ag] 2+ Unit-Encapsulated Trimetallic Cages: One-pot Syntheses and Modulation of Argentophilic Interactions by the Uncoordinated Substituents Guo-Xia Jin,,a Gui-Ying Zhu,,a Yan-Yan Sun, c Qing-Xiu Shi, a Li-Ping Liang, a Hai-Ying Wang, b Xiang-Wen Wu, a and Jian-Ping Ma*,a a College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging, Key Laboratory of Molecular and ano Probes, Ministry of Education, Shandong ormal University, Jinan 250014, People s Republic of China b College of Chemistry and Materials Science, Sichuan ormal University, Chengdu 610066, People s Republic of China c QiLu Pharmaceutical (Haian) Co., Ltd., Haikou, Hainan 570314, People s Republic of China These authors contributed equally. Experimental General methods Chemicals and solvents used in the syntheses were obtained from commercial sources and used without further purification. 1 H MR data were collected using a BRUKER AVACE 400 spectrometer. Chemical shifts are reported in δ relative to TMS. Element analyses were performed on a Perkin-Elmer Model 240C analyzer. Infrared (IR) spectra were obtained in the 400-4000 cm -1 range using a BIO-RAD FTS-40 infrared spectrometer. Powder X-ray diffraction patterns were collected using a Bruker D8 ADVACE diffractometer (Cu K = 1.540598 Å) with an operating power of 40 Kv and fixed divergence slit of 0.76 mm. The data were collected in the range of 2θ = 5-50. Photoluminescence spectra were measured on a FLS920 Fluorescence Spectrophotometer (slit width: 5 nm; sensitivity: high). 4-amino-3-(2-pyridyl)-5-mercapto-1,2,4-triazole (S3) 1 and 1,3,5-tris(bromomethyl)-2,4,6-trimethyl benzene (S4) 2 were prepared according to a modified S1

method in literature. O CHH 2 KOH, CS 2 EtOH O S H 2 H 2 H 2 O CHHCS - K + H 2 SH H 2 S1 S2 S3 KOH S Br H 2 (HCHO) n, KBr H 2 SO 4, HOAc Br Br S S H 2 L S4 Synthesis of 1,3,5-tris(4-amino-5-pyridin-2-yl-1,2,4-triazol-3-ylmercaptomethyl)-2,4,6-trimethyl benzene (L) S3 (11.59 g, 60 mmol) and KOH (5.9 g, 120 mmol) were dissolved in 100 ml methanol and stirred at room temperature for 20 min. 1, 3, 5-tris(bromomethyl)-2, 4, 6-trimethyl benzene S4 (3.99 g, 10 mmol) was added and the mixture was stirred at room temperature for 24 h. The solvent was removed by rotary evaporation. The crude product was further purified by chromatography on a silica gel column with dichloromethane/methanol (20:1, v/v) to give a white solid after solvent removal under vacuum. Yield: 5.48 g (75%). 1 H MR (400 MHz, 25 o C, DMSO-d 6, ppm): 8.73 (d, J = 4 Hz, 6H, -C 5 H 4 ); 8.13 (d, J = 8 Hz, 6H, -C 5 H 4 ); 8.02 (t, J = 8 Hz, 6H, -C 5 H 4 ); 7.54 (t, J = 8 Hz, 6H, -C 5 H 4 ); 6.65 (s, 12H, -H 2 ); 4.58 (s, 12H, -SCH 2 -); 2.53 (s, 18H, -CH 3 ). IR (cm -1 ): 3276 (s), 3171 (s), 3053 (w), 2966 (w), 1625 (m), 1591 (s), 1567 (m), 1450 (vs), 1422 (s), 1356 (m), 1010 (s), 789 (s), 729 (m). Preparation of complex [Ag 5 (L) 2 (SbF 6 ) 5 ] 3C 4 H 8 O 2 (1) A solution of AgSbF 6 (10 mg, 0.0291 mmol) in ethanol(7 ml) was layered carefully onto a solution of L (10 mg, 0.0136 mmol) in 1,4-dioxane (6 ml) in a 1.5-cm in diameter glass tube. The solution was left for a week at room temperature, and colorless crystals were collected (11.5 mg, 57%). 2.1 equiv. of Ag(I) is the most suitable ratio for obtaining the single-crystals 1 of the best quality. 1 H MR (400 MHz, 25 o C, DMSO-d 6, ppm): 8.79 (d, J = 4 Hz, 6H, -C 5 H 4 ); 8.27 (d, J = 8 Hz, 6H, -C 5 H 4 ); 8.09 (t, J = 8 Hz, 6H, -C 5 H 4 ); 7.63 (t, J = 8 Hz, 6H, -C 5 H 4 ); 6.89 (s, 12H, -H 2 ); 4.45 (s, 12H, -SCH 2 -); 2.18 (s, 18H, -CH 3 ). IR (cm -1 ): 3636 (w), 3342 (w), 3186 (w), 1625 (m), 1593 (m), 1475 (m), 1444 (s), 1009 (m), 783 (m), 660 (vs). Elemental analysis Calcd (%) for C 78 H 90 30 O 6 S 6 Ag 5 Sb 5 F 30 : C 30.46, H 2.95, 1.37; S2

Found: C 30.90, H 3.43, 1.55. Preparation of complex [Ag 5 (L 1 ) 2 (BF 4 ) 5 ] 2(C 3 H 6 O) 5(CHCl 3 ) (2) A solution of AgBF 4 (4 mg, 0.0206 mmol) in acetone (7 ml) was layered carefully onto a solution of L (10 mg, 0.0136 mmol) in CHCl 3 (6 ml) in a 1.5-cm in diameter glass tube. The solution was left for a week at room temperature, and colorless crystals were collected (8.4 mg, 64%). 1.5 equiv. of Ag(I) is the most suitable ratio for obtaining the single-crystals 2 of the best quality. 1 H MR (400 MHz, 25 o C, DMSO-d 6, ppm): 8.71 (d, J = 4 Hz, 6H, -C 5 H 4 ); 8.04 (d, J = 4 Hz, 12H, -C 5 H 4 ); 7.58 (q, J = 4 Hz, 6H, -C 5 H 4 ); 4.40 (s, 12H, -SCH 2 -); 2.33 (s, 18H, -CH 3 ); 2.22 (br. s, 18H, -CH 3 ); 1.86 (s, 18H, -CH 3 ). IR (cm -1 ): 3020 (w), 1710 (w), 1625 (m), 1596 (m), 1475 (m), 1433 (s), 1373 (m), 1060 (vs), 621 (s). Elemental analysis Calcd (%) for C 95 H 107 Ag 5 30 O 2 S 6 Cl 15 F 20 B 5 : C 37.78, H 3.57, 1.39; Found: C 38.01, H 3.91, 1.69. Preparation of complex [Ag 5 (L 1 ) 2 (ClO 4 ) 5 ] 2(C 3 H 6 O) 5(CHCl 3 ) (3) AgClO 4 (5 mg, 0.0241 mmol) was used instead of AgBF 4, colorless needle crystals were collected (8.2 mg, 52%). 1 H MR (400 MHz, 25 o C, DMSO-d 6, ppm): 8.69 (d, J = 4 Hz, 6H, -C 5 H 4 ); 8.06 8.02 (m, 12H, -C 5 H 4 ); 7.56 (t, 6H, -C 5 H 4 ); 4.42 (s, 12H, -SCH 2 -); 2.31 (s, 18H, -CH 3 ); 2.26 (br. s, 18H, -CH 3 ); 1.86 (s, 18H, -CH 3 ). IR (cm -1 ): 3021 (w), 1710 (w), 1626 (m), 1596 (m), 1470 (m), 1428 (s), 1373 (m), 1090 (vs), 621 (s). Elemental analysis Calcd (%) for C 95 H 107 Ag 5 30 O 22 S 6 Cl 20 : C 37.00, H 3.50, 1.36; Found: C 37.10, H 3.85, 1.30. Preparation of complex [Ag 5 (L 2 ) 2 (ClO 4 ) 5 ] (C 4 H 8 O 2 ) (solvent) (4) A solution of AgClO 4 (7 mg, 0.034 mmol) in cyclohexanone (7 ml) was layered carefully onto a solution of L (10 mg, 0.0136 mmol) in 1,4-dioxane (6 ml) and chloroform (1 ml) in a 1.5-cm in diameter glass tube. The solution was left for 5 days at room temperature, and pale yellow crystals were collected (16.5 mg, 79%). 1 H MR (400 MHz, 25 o C, DMSO-d 6, ppm): 8.70 (d, J = 4 Hz, 6H, -C 5 H 4 ); 8.03 (s, 12H, -C 5 H 4 ); 7.58 (s, 6H, -C 5 H 4 ); 4.41 (br. s, 12H, -SCH 2 -); 2.61 (s, 12H, -CH 2 ), 2.25 (t, 12H, -CH 2 ), 2.11 (s, 18H, -CH 3 ), 1.82 1.53 (m, 36H, -CH 2 ). IR (cm -1 ): 3021 (w), 2940 (w), 2862 (w), 1700 (w), 1616 (m), 1596 (m), 1470 (m), 1431 (s), 1089 (vs), 622 (s). Elemental analysis Calcd (%) for C 106 H 122 Ag 5 Cl 5 30 O 22 S 6 C: 47.17, H 4.56, 1.56; Found: C 46.95, H 4.40, 1.63. S3

Figure S1. 1 H MR spectrum of ligand L. Figure S2. 1 H MR spectrum of complex 1. S4

Figure S3. 1 H MR spectrum of complex 2. Figure S4. 1 H MR spectrum of complex 3. S5

Figure S5. 1 H MR spectrum of complex 4. Figure S6. ORTEP figure of complex 1. S6

Figure S7. Ball-and-stick model of cage 1, showing the Ag- and Ag π interactions. Figure S8. ORTEP figure of complex 2. S7

Figure S9. ORTEP figure of complex 3. Figure S10. ORTEP figure of complex 4. S8

Figure S11. Titration experiments by the addition of a solution of AgSbF 6 into a solution of L in DMSO-d 6. S9

Table S1. Crystal data and structure refinement for 1-4. 1 2 Chemical formula C 78 H 90 30 O 6 S 6 Ag 5 Sb 5 F 30 C 95 H 107 Ag 5 B 5 Cl 15 F 20 30 O 2 S 6 Formula weight 3454.26 3398.62 Temperature/K 150.00(10) 150.00(10) Wavelength/ Å 1.54184 1.54184 Crystal system Monoclinic Monoclinic Space group C2/c C2/c a/å 13.0565(3) 13.4980(6) b/å 33.8016(11) 55.318(4) c/å 31.3627(8) 17.5604(8) α/ 90 90 β/ 100.988(3) 90.810(4) γ/ 90 90 Volume/ Å 3 13587.6(6) 13110.7(12) Z 4 4 ρ calc / g cm 3 1.689 1.722 μ/ mm 1 15.083 10.343 F(000) 6688.0 6776.0 Reflections collected/ 40976/12030 43718/ 11688 unique [R int = 0.1038] [R int = 0.0576] Data/ parameter restraints/ 12030/91/723 11688/32/815 GOOF 1.229 1.098 R[I>2sigma(I)] R 1 = 0.1150, wr 2 = 0.2962 R 1 = 0.0803, wr 2 = 0.2156 R(all data) R 1 = 0.1435, wr 2 = 0.3263 R 1 = 0.1044, wr 2 = 0.2552 S10

3 4 Chemical formula C 95 H 107 Ag 5 30 O 22 S 6 Cl 20 C 106 H 122 Ag 5 Cl 5 30 O 22 S 6 Formula weight 3461.82 3077.29 Temperature/K 150.00(10) 173(2) Wavelength/ Å 1.54184 1.54178 Crystal system Monoclinic Monoclinic Space group C2/c P2 1 /c a/å 13.5479(7) 27.0615(4) b/å 55.325(3) 29.3607(5) c/å 17.6923(9) 36.1187(8) α/ 90 90 β/ 90.842(6) 98.104(2) γ/ 90 90 Volume/ Å 3 13259.7(11) 28411.3(9) Z 4 8 ρ calc / g cm 3 1.734 1.439 μ/ mm 1 11.044 7.701 F(000) 6936.0 12480.0 Reflections collected/ 25267/11800 111966/53714 unique [R int = 0.0668] [R int = 0.0133] Data/ restraints/ parameter 11800/26/823 53714/2/3135 GOOF 1.047 1.013 R[I>2sigma(I)] R 1 = 0.0806, wr 2 = 0.2215 R1 = 0.0406, wr2 = 0.1051 R(all data) R 1 = 0.0961, wr 2 = 0.2489 R1 = 0.0554, wr2 = 0.1090 Table S2. Selected bond lengths (Å) and angles (ᵒ) in complexes 1-4. 1 Ag1' 11' 2.30(3) Ag2 1 2.395(9) Ag1 7 1 2.237(16) Ag2 2 2.343(8) S11

Ag1 10 1 2.326(16) Ag3 3 2.211(8) Ag1 12 2.309(15) Ag3 6 2.213(9) 7 1 Ag1 11 151.1(8) Ag3 13 2.204(9) 7 1 Ag1 10 1 72.7(5) 2 Ag2 1 69.4(3) 7 1 Ag1 12 122.2(6) 2 Ag2 2 1 119.5(4) 12 Ag1 10 1 150.7(6) 1 1 Ag2 1 114.8(5) 10 1 Ag1 11 112.1(9) 2 1 Ag2 1 153.4(3) 12 Ag1 11 68.3(7) 3 Ag3 6 118.5(3) 13 Ag3 3 122.7(4) 13 Ag3 6 118.7(4) 2 Ag(1) Ag(1) 1 3.3413(12) Ag(1) (3) 2.233(6) Ag(1) (8) 2.265(6) Ag(1) (13) 2.262(6) Ag(2) (1) 2.363(7) Ag(2) (2) 2.299(7) Ag(2) (6) 1 2.382(8) Ag(2) (7) 1 2.274(6) Ag(3) (11) 2.421(7) Ag(3) (12) 2.265(7) (13) Ag(1) (8) 116.0(2) (2) Ag(2) (1) 71.2(2) (3) Ag(1) (8) 123.1(3) (1) Ag(2) (6) 1 108.5(3) (3) Ag(1) (13) 120.9(3) (2) Ag(2) (6) 1 156.1(3) (12) Ag(3) (11) 1 155.6(3) (7) 1 Ag(2) (2) 120.2(2) (12) 1 Ag(3) (11) 155.6(3) (7) 1 Ag(2) (1) 154.6(3) (12) 1 Ag(3) (12) 127.4(3) (7) 1 Ag(2) (6) 1 70.7(2) (11) 1 Ag(3) (11) 98.4(4) (12) Ag(3) (11) 70.6(2) (12) 1 Ag(3) (11) 1 70.6(2) 3 Ag(1) Ag(1) 1 3.3260(11) Ag(2) (1) 2.378(7) Ag(1) (3) 2.233(6) Ag(2) (2) 2.294(6) Ag(1) (8) 2.267(6) Ag(2) (6) 1 2.388(7) Ag(1) (13) 2.261(6) Ag(2) (7) 1 2.265(6) Ag(3) (11) 2.393(7) Ag(3) (12) 2.262(7) S12

(3) Ag(1) (8) 123.2(2) (1) Ag(2) (6) 1 108.9(3) (3) Ag(1) (13) 121.1(2) (2) Ag(2) (1) 71.4(2) (13) Ag(1) (8) 115.7(2) (2) Ag(2) (6) 1 156.6(3) (11) Ag(3) (11) 1 99.6(3) (7) 1 Ag(2) (1) 152.8(2) (12) Ag(3) (11) 71.1(2) (7) 1 Ag(2) (2) 120.0(2) (12) 1 Ag(3) (11) 156.4(2) (7) 1 Ag(2) (6) 1 70.8(2) (12) 1 Ag(3) (12) 125.3(3) 4 Ag1 Ag2 3.1226(3) Ag1 1 2.220(3) Ag1 6 2.274(2) Ag1 11 2.179(3) Ag2 26 2.210(2) Ag2 16 2.223(3) Ag2 21 2.296(3) Ag3 12 2.278(3) Ag3 27 2.346(2) Ag3 30 2.346(2) Ag3 15 2.507(2) Ag4 22 2.262(2) Ag4 2 2.308(2) Ag4 5 2.350(3) Ag4 25 2.408(2) Ag5 7 2.325(3) Ag5 20 2.372(3) Ag5 10 2.401(3) Ag5 17 2.403(2) 11 Ag1 1 121.69(9) 11 Ag1 6 122.81(9) 1 Ag1 6 115.44(9) 11 Ag1 Ag2 88.70(6) 1 Ag1 Ag2 92.40(6) 6 Ag1 Ag2 91.66(6) 26 Ag2 16 123.49(10) 26 Ag2 21 119.36(10) 16 Ag2 21 116.79(10) 26 Ag2 Ag1 89.09(6) 12 Ag3 27 116.48(9) 12 Ag3 30 163.46(9) 27 Ag3 30 70.77(9) 12 Ag3 15 69.47(8) 22 Ag4 2 122.13(9) 2 Ag4 5 72.34(9) 22 Ag4 25 70.11(9) 5 Ag4 25 103.07(10) 7 Ag5 10 71.21(10) 20 Ag5 10 102.95(10) 7 Ag5 17 117.91(9) S13

20 Ag5 17 70.96(9) 10 Ag5 17 160.70(11) Symmetry transformations used to generate equivalent atoms: 1: 1 -X, +Y, 1/2-Z; 2 1-X, 2-Y, 1-Z; 3 1-X, +Y, 1/2-Z. 2: 1 2-X, +Y, 1/2-Z; 2 -X, +Y, 1/2-Z; 3 1-X, +Y, 1/2-Z. 3: 1 2-X, +Y, 1/2-Z; 2 -X, +Y, 1/2-Z; 3 1-X, +Y, 1/2-Z. Reference 1. Reid, J. R.; Heindel,. D. Improved syntheses of 5-substituted-4-amino-3-mercapto-(4H)-1,2,4-triazoles. J. Heterocyclic Chem. 1976, 13, 925 926. 2. Liu, G.; Wang, Y.; Shen, C.; Ju, Z.; Yuan, D. A facile synthesis of microporous organic polymers for efficient gas storage and separation J. Mater. Chem. A 2015, 3, 3051 3058. S14