S1

Electronic Supplementary Information (ESI)

Structure, Solution Assembly, Electroconductivity of Nanosized Argento-

Organic-Cluster/Framework Templated by Chromate

Xiao-Yu Li,ǂa Hai-Feng Su,ǂb Mohamedally Kurmoo,c Chen-Ho Tung,a and Di Sun*,a and Lan-Sun Zhengb

aKey Lab of Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical

Engineering, Shandong University, Jinan, 250100, P. R. China.

bState Key Laboratory for Physical Chemistry of Solid Surfaces and Department of Chemistry, College of

Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China.

cInstitut de Chimie de Strasbourg, Université de Strasbourg, CNRS-UMR 7177, 4 rue Blaise Pascal, 67008

Strasbourg Cedex, France.

ǂ These authors contributed equally to this work.

*Corresponding author. E-mail: dsun@sdu.edu.cn.

Electronic Supplementary Material (ESI) for Nanoscale.This journal is © The Royal Society of Chemistry 2017

S2

Experiment details

The precursors of {(HNEt3)2[Ag10(SC6H4tBu)12]}n (K. Tang et. al., Eur. J. Inorg. Chem.

2004, 78) and [AgiBuS]n (S. Q. Zang, et. al., Chem.-Eur. J., 2014, 20, 12416-12420) were

prepared according to the literature with some modifications. All chemicals and solvents used

in the syntheses were of analytical grade and used without further purification. IR spectra were

recorded on a PerkinElmer Spectrum Two in the frequency range of 4000-400 cm-1. The

elemental analyses (C, H, N contents) were determined on a Vario EL III analyzer. Powder X-

ray diffraction (PXRD) data were collected on a Philips X’Pert Pro MPD X-ray diffractometer

with Cu Kα radiation equipped with an X’Celerator detector. Thermogravimetric analyses

(TGA) were performed on a Netzsch STA 449C thermal analyzer from room temperature to

800 °C under nitrogen atmosphere at a heating rate of 10 °C/min.The diffuse-reflectance

spectra were performed on UV−Vis spectrophotometer (Evolution 220, ISA-220 accessory,

Thermo Scientific) using a built-in 10 mm silicon photodiode with a 60 mm Spectralon sphere.

Electrochemical measurements were performed with a CHI660E electrochemical workstation.

A conventional three-electrode system was used. The working electrode was a carbon paste

electrode (CPE), a Pt wire as the counter electrode and Ag/AgCl (3 M KCl) reference electrode.

The DC current-voltage (I-V) measurements were performed at room temperature using two-

probe method on an Agilent B1500A semiconductor parameter analyzer. The high-resolution

electrospray mass spectrometry was performedon an Agilent (Santa Clara, CA, USA) ESI-TOF

mass spectrometer (6224). The instrument was calibrated with an Agilent tune mixture before

mass analysis. The compressed circular pellet samples were made as following: the single

crystals of 1-3 were ground and pressed into pellets 0.4 cm in diameter, with thickness of

0.04−0.07 cm. The measurements were performed on these circular pellet samples with silver

paint coated on both sides as electrodes. We repeated experiments on samples with different

thicknesses. The observed results are consistent within experimental errors.

S3

X-ray Crystallography

Single crystals of 1, 3 and 4 with appropriate dimensions were chosen under an optical

microscope and quickly coated with high vacuum grease (Dow Corning Corporation)

before being mounted on a glass fiber for data collections. Single-crystal X-ray

diffraction data were collected using a Bruker SMART APEX II diffractometer with a

CCD area detector (graphite monochromatic Mo Kα radiation, λ = 0.71073 Å, ω-scans

with a 0.5° step in ω). Indexing was performed using APEX2 (Difference Vectors

method).[1] Data integration and reduction were performed using Saint Plus 6.01.[2]

Absorption correction was performed by multi-scan method implemented in

SADABS.[3] Space groups were determined using XPREP implemented in APEX2.[4]

The data of 2 were collected on an Agilent Technologies SuperNova A diffractometer

using Cu radiation with an Oxford Cryosystems Cryostream low-temperature device

operating at 100 K. Data were processed using the CrysAlisPro software package

(Agilent Technologies 2013, CrysAlisPro Software system, version 1.171.35.19,

Agilent Technologies UK Ltd, Oxford, UK). Structures of 1-4 were solved using

SHELXS-97 (direct methods) and refined using SHELXL-97 (full-matrix least-squares

on F2).[5] Hydrogen atoms were placed in calculated positions and included as riding

atoms with isotropic displacement parameters 1.2-1.5 times Ueq of the attached C

atoms. Furthermore, it was necessary to use constraints to control the geometry of the

alkyl chain and restraints to enforce chemically sensible bond lengths and angles.

Vibrational restraints were also used to control atomic displacement parameters of

various atoms. All structures were examined using the Addsym subroutine of

PLATON[6] to assure that no additional symmetry could be applied to the models.

Pertinent crystallographic data collection and refinement parameters of 1-4 are collated

in Table S1. Selected bond lengths and angles are collated in Table S2.

[1] Bruker APEX2; Bruker AXS, Inc.: Madison, WI, 2010.

[2] Bruker SAINT, Data Reduction Software; Bruker AXS, Inc.: Madison, WI, 2009.

[3] G. M. Sheldrick, SADABS, Program for Empirical Absorption Correction;

University of Gottingen: Gottingen, Germany, 2008.

S4

[4] a) G. M. Sheldrick, SHELXL-97, Program for the Refinement of Crystal;

University of Gottingen: Gottingen, Germany, 1997. b) G. M. Sheldrick, Acta

Crystallogr.1990, A46, 467. c) G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112.

[5] A. L. Spek, Implemented as the PLATON Procedure, a Multipurpose

Crystallographic Tool, Utrecht University, Utrecht, The Netherlands, 1998.

S5

Synthesis of {(HNEt3)3[(CrO4)4@Ag47(SC6H4tBu)24(CF3COO)18(DMF)4]} (1)

The precursor {(HNEt3)2[Ag10(SC6H4tBu)12]}n (13.7 mg, 0.05 mmol),

AgCOOCF3 (22.1 mg, 0.10 mmol), K2Cr2O7 (1.5 mg, 0.005 mmol) and 1,10-

phenanthroline (1.80 mg, 0.01 mmol) were mixed with mixture solution of DMF-

CH2Cl2-CH3OH (4 mL, 1:3:3). The resulting solution was sealed in a 25 mL Teflon-

lined reaction vessel and heated to 65 °C within 5 hours, and kept at 65 °C for 33

hours, then slowly cooled to 30 °C for 13 hours. Finally the solution was filtered

and the filtrate was slowly evaporated in darkness at room temperature. Complex 1

crystallized as red-block crystals during one week (yield: 42 %). Elemental analyses

calc. (found) for 1: C306H388Ag47Cr4F54N7O56S24: C, 45.37 (45.40); H, 4.82 (4.79);

N, 0.61 (0.68) %. Selected IR peaks (cm−1): 2961 (m), 2906 (w), 2870 (w), 1634 (s),

1484 (m), 1392 (m), 1269 (w), 1194 (s), 1136 (s), 1010 (m), 825 (s), 793 (m), 721

(s), 660 (w), 547 (m).

Synthesis of [(CrO4)5@Ag40(SiBu)27(CF3COO)3]n (2)

The precursor [AgiBuS]n (19.4 mg, 0.10 mmol), AgCOOCF3 (11.0 mg, 0.05 mmol),

K2Cr2O7 (1.5 mg, 0.005 mmol) and 2,2’-bipyridine (1.6 mg, 0.01 mmol) were mixed

with mixture solution of DMF-CH3OH (5 mL, 1:4). The resulting solution was

sealed in a 25 mL Teflon-lined reaction vessel and heated to 65 °C for 5 hours, kept

at 65 °C for 33 hours, then slowly cooled to 30 °C for 13 hours. Red-rod crystals of

2 were isolated by filtration, washed with EtOH, and dried in air (yield: 28 %).

Elemental analyses calc. (found) for 2: C114H243Ag40Cr5F9O26S27: C, 17.92 (17.98);

H, 3.21 (3.18) %. Selected IR peaks (cm−1): 2955 (m), 2910 (w), 2873 (w), 1660 (s),

1452 (m), 1369 (m), 1274 (w), 1197 (s), 1134 (s), 1043 (m), 1010 (w), 952 (w), 819

(s), 793 (s), 720 (s), 664 (m), 607 (w), 521 (w).

S6

Synthesis of [(CrO4)2@Ag41(SiBu)30(NO3)3(CN)4]n (3)

The synthesis of complex 3 was similar to that of 2 except that AgNO3 (8.5 mg, 0.05

mmol) and CH3CN (5 mL) instead of AgCOOCF3 (11.0 mg, 0.05 mmol) and DMF-

CH3OH (5 mL, 1:4) were used. Orange rod crystals of 3 were isolated by filtration,

washed with EtOH, and dried in air (yield: 35 %). Elemental analyses calc. (found)

for 3:C124H270Ag41Cr2N7O17S30: C, 19.54 (19.60); H, 3.57 (3.62); N, 1.29 (1.20) %.

Selected IR peaks (cm−1): 2953 (s), 2909 (w), 2868 (w), 2138 (m), 1445 (m), 1367

(m), 1290 (m), 1139 (m), 1051 (w), 1009 (w), 951 (w), 820 (s), 665 (m), 603 (w).

Synthesis of [CrO4@Ag20(SiPr)10(Cr2O7)2(COOCF3)4(DMF)4]n (4)

The synthesis of 4 was similar to that of 2 except using the precursor [AgiPrS]n (9.2

mg, 0.05 mmol) instead of the [AgiBuS]n (19.4 mg, 0.10 mmol). In addition, 2,2-

bipy (1.6 mg, 0.01 mmol) was not added into the reaction mixture. Red block

crystals of 4 were isolated by filtration, washed with EtOH, and dried in air (yield:

8 %). Elemental analyses calc. (found) for 4: C50H98Ag20Cr5F12N4O30S10: C, 14.29

(14.33); H, 2.35 (2.29); N, 1.33 (1.36) %.

S7

Scheme S1: Solvothermal synthetic route for 1-4.

S8

Table S1: Selected bond distances (Å) and angles (°) for 1-4

Compound 1Ag1—O1 2.00 (4) Ag14—S5 2.483 (9)Ag1—O1i 2.00 (4) Ag16—S8 2.614 (7)Ag1—O1ii 2.00 (4) Ag16—S9 2.641 (7)Ag1—O1iii 2.00 (4) Ag16—S7 2.654 (8)Ag2—S5ii 2.545 (7) Ag17—O19iv 2.352 (15)Ag2—S5 2.545 (7) Ag17—O19 2.352 (15)Ag2—O1 2.60 (3) Ag17—S9 2.512 (7)Ag2—O1ii 2.60 (3) Ag17—S9iv 2.512 (7)

Ag2—Ag14 2.950 (3) Ag17—Ag18 2.916 (3)Ag2—Ag14ii 2.950 (3) Ag17—Ag18iv 2.916 (3)

Ag3—S1i 2.590 (7) Ag18—O27 2.35 (2)Ag3—S2 2.655 (8) Ag18—S11 2.470 (8)Ag3—S5ii 2.660 (8) Ag18—S9 2.513 (7)Ag4—O8 2.37 (3) Ag18—Ag19 3.001 (3)Ag4—S2 2.538 (7) Ag18—Ag20 3.007 (3)Ag4—S6 2.600 (7) Ag19—S9 2.420 (7)

Ag4—Ag6 3.018 (4) Ag19—S10 2.441 (8)Ag4—Ag7 3.028 (3) Ag19—Ag20 2.996 (4)Ag5—O4 2.360 (18) Ag20—O26 2.38 (6)Ag5—O4i 2.360 (18) Ag20—O28 2.50 (4)Ag5—S2 2.509 (7) Ag20—S11 2.526 (7)Ag5—S2i 2.509 (7) Ag20—S10 2.582 (6)

Ag5—Ag6i 3.003 (3) Ag20—Ag22 3.025 (4)Ag5—Ag6 3.003 (3) Ag20—Ag21 3.069 (3)Ag6—O29 2.43 (8) Ag21—S12 2.508 (8)Ag6—S3 2.463 (7) Ag21—S10 2.515 (8)Ag6—S2 2.468 (7) Ag21—O25 2.61 (7)

Ag6—Ag7 3.035 (3) Ag21—Ag23 2.970 (3)Ag7—O7 2.37 (3) Ag21—Ag24 3.070 (3)Ag7—O9 2.47 (3) Ag21—Ag22 3.089 (3)Ag7—S6 2.488 (9) Ag22—O18 2.30 (3)Ag7—S3 2.526 (8) Ag22—S11 2.466 (8)

Ag7—Ag12 3.100 (4) Ag22—S12 2.522 (7)Ag7—Ag9 3.167 (4) Ag22—Ag28 3.090 (3)Ag8—S1 2.439 (9) Ag22—Ag27 3.117 (3)Ag8—S3 2.456 (9) Ag23—S8ii 2.441 (7)

Ag8—Ag9 2.958 (4) Ag23—S12 2.469 (7)Ag8—Ag10 3.014 (4) Ag23—O20 2.470 (16)Ag9—O10 2.34 (4) Ag23—Ag24 3.008 (4)

S9

Ag9—S4 2.491 (8) Ag24—O23 2.33 (2)Ag9—S3 2.529 (9) Ag24—S10 2.491 (6)

Ag9—O14 2.60 (5) Ag24—S8ii 2.531 (6)Ag9—Ag10 3.019 (4) Ag24—Ag25 2.897 (3)Ag9—Ag12 3.060 (4) Ag25—O21ii 2.439 (18)Ag10—O13 2.367 (19) Ag25—O21 2.439 (18)Ag10—S4 2.493 (7) Ag25—S8 2.538 (7)Ag10—S1 2.527 (7) Ag25—S8ii 2.538 (7)

Ag10—Ag11 2.939 (3) Ag25—Ag24ii 2.897 (3)Ag11—O2 2.28 (3) Ag26—O22v 2.43 (2)

Ag11—O2iii 2.28 (3) Ag26—O22 2.43 (2)Ag11—S1 2.540 (9) Ag26—S7iv 2.489 (6)

Ag11—S1iii 2.540 (9) Ag26—S7ii 2.489 (6)Ag11—Ag10iii 2.939 (3) Ag26—Ag27 3.166 (3)

Ag12—O11 2.44 (5) Ag26—Ag27v 3.166 (3)Ag12—S4 2.502 (7) Ag27—O5 2.41 (9)Ag12—S6 2.552 (7) Ag27—S12 2.493 (8)

Ag12—Ag13 3.041 (4) Ag27—O6 2.50 (9)Ag12—Ag14 3.088 (3) Ag27—S7iv 2.505 (8)

Ag13—S5 2.507 (7) Ag27—Ag28 2.985 (3)Ag13—S4 2.567 (7) Ag28—O17 2.37 (3)

Ag13—C76iii 2.66 (3) Ag28—S7iv 2.578 (6)Ag13—Ag14 2.951 (3) Ag28—C26iv 2.68 (3)Ag14—O12 2.41 (3) Ag28—S11 2.684 (7)Ag14—S6 2.460 (9)

O1—Ag1—O1i 138.0(16) S5—Ag13—C76iii 107.4(7)O1—Ag1—O1ii 50.9(16) S4—Ag13—C76iii 86.9(7)O1i—Ag1—O1ii 152.6(14) O12—Ag14—S6 110.7(9)O1—Ag1—O1iii 152.6(14) O12—Ag14—S5 95.2(9)O1i—Ag1—O1iii 50.9(16) S6—Ag14—S5 148.1(3)O1ii—Ag1—O1iii 138.0(16) S8—Ag16—S9 103.5(2)S5ii—Ag2—S5 175.4(4) S8—Ag16—S7 112.8(2)S5ii—Ag2—O1 95.5(6) S9—Ag16—S7 104.3(2)S5—Ag2—O1 88.8(6) O19iv—Ag17—O19 125.9(8)

S5ii—Ag2—O1ii 88.8(6) O19iv—Ag17—S9 86.2(4)S5—Ag2—O1ii 95.5(6) O19—Ag17—S9 96.5(4)O1—Ag2—O1ii 38.6(17) O19iv—Ag17—S9iv 96.5(4)

Si—Ag3—S2 105.5(3) O19—Ag17—S9iv 86.2(4)Si—Ag3—S5ii 102.1(2) S9—Ag17—S9iv 174.1(3)S2—Ag3—S5ii 109.8(2) O27—Ag18—S11 110.8(6)O8—Ag4—S2 106.3(8) O27—Ag18—S9 97.9(6)O8—Ag4—S6 97.9(7) S11—Ag18—S9 144.6(2)S2—Ag4—S6 147.9(2) S9—Ag19—S10 157.5(3)

S10

O4—Ag5—O4i 102.0(9) O26—Ag20—O28 79.7(18)O4—Ag5—S2 90.9(5) O26—Ag20—S11 118.1(15)O4i—Ag5—S2 93.3(5) O28—Ag20—S11 106.3(11)O4—Ag5—S2i 93.3(5) O26—Ag20—S10 96.3(14)O4i—Ag5—S2i 90.9(5) O28—Ag20—S10 97.8(11)S2—Ag5—S2i 173.4(4) S11—Ag20—S10 140.6(2)O29—Ag6—S3 101(3) O18—Ag22—S11 110.1(10)O29—Ag6—S2 107(3) O18—Ag22—S12 96.9(9)S3—Ag6—S2 144.0(3) S11—Ag22—S12 142.3(2)O7—Ag7—O9 98.5(14) S8ii—Ag23—S12 162.7(3)O7—Ag7—S6 106.7(8) S8ii—Ag23—O20 94.3(4)O9—Ag7—S6 103.8(12) S12—Ag23—O20 70.6(4)O7—Ag7—S3 101.2(8) O23—Ag24—S10 112.2(6)O9—Ag7—S3 99.7(9) O23—Ag24—S8ii 98.9(6)S6—Ag7—S3 140.0(3) S10—Ag24—S8ii 140.8(2)S1—Ag8—S3 156.1(3) S8—Ag25—S8ii 170.7(3)

O10—Ag9—S4 111.3(13) O22v—Ag26—O22 107.0(10)O10—Ag9—S3 100.8(12) O22v—Ag26—S7 94.1(4)S4—Ag9—S3 142.6(3) O22—Ag26—S7iv 91.0(4)

O10—Ag9—O14 78.0(13) O22v—Ag26—S7ii 91.0(4)S4—Ag9—O14 107.5(11) O22—Ag26—S7ii 94.1(4)S3—Ag9—O14 97.3(11) S7iv—Ag26—S7ii 171.4(4)O13—Ag10—S4 110.6(5) O5—Ag27—S12 113(2)O13—Ag10—S1 96.7(5) O5—Ag27—O6 43.9(14)S4—Ag10—S1 144.8(2) S12—Ag27—O6 109.3(18)

O2—Ag11—O2iii 125.6(16) O5—Ag27—S7iv 101(2)O2—Ag11—S1 86.8(5) S12—Ag27—S7 v 146.0(3)

O2iii—Ag11—S1 97.0(5) O6—Ag27—S7iv 96.1(18)O2—Ag11—S1iii 97.0(5) O17—Ag28—S7iv 104.7(7)

O2iii—Ag11—S1iii 86.8(5) O17—Ag28—C26iv 99.1(11)S1—Ag11—S1iii 171.8(3) S7iv—Ag28—C26iv 111.1(6)O11—Ag12—S4 103.3(16) O17—Ag28—S11 100.7(7)O11—Ag12—S6 100.7(16) S7iv—Ag28—S11 145.7(2)S4—Ag12—S6 139.8(2) C26iv—Ag28—S11 86.8(6)S5—Ag13—S4 150.1(3)

Symmetry codes: (i) x, −y+1/4, −z+5/4; (ii) −x+5/4, y, −z+5/4; (iii) −x+5/4, −y+1/4, z; (iv) −x+5/4, −y+5/4, z; (v) x, −y+5/4, −z+5/4.

Compound 2Ag1—S12i 2.06(3) Ag10—S1ii 2.457(4)Ag1—S14 2.360(12) Ag10—S10 2.717(4)Ag1—S12 2.37(2) Ag10—Ag13 3.1379(16)Ag1—Ag2 3.218(5) Ag11—S4 2.447(4)Ag1—Ag3 3.197(5) Ag11—S3 2.460(3)

S11

Ag2—O8 2.512(11) Ag11—O11i 2.547(12)Ag2—S13 2.534(5) Ag11—S8 2.838(4)Ag2—S12i 2.576(17) Ag12—S4 2.378(6)Ag2—S9 2.632(6) Ag12—S6i 2.386(6)Ag3—S14 2.367(12) Ag13—S10 2.399(4)Ag3—S7i 2.720(7) Ag13—S8 2.416(4)

Ag3—Ag17i 2.889(4) Ag13—Ag15 3.0364(15)Ag3—Ag16i 2.934(4) Ag13—Ag14 3.1641(17)Ag3—Ag4 3.086(4) Ag14—S13 2.408(4)Ag4—S11 2.429(4) Ag14—S10 2.430(4)Ag4—S13 2.440(4) Ag15—S9 2.413(4)Ag4—O5 2.505(13) Ag15—S8 2.422(4)Ag5—S1 2.355(4) Ag15—O10i 2.519 (10)Ag5—S11 2.359(4) Ag15—Ag16 3.0728(17)Ag5—O4 2.504(9) Ag15—Ag19 3.2130(15)Ag5—Ag6 3.3475(19) Ag16—S7 2.363(5)Ag6—O2 2.41(2) Ag16—S9 2.380(4)Ag6—S1 2.456(5) Ag17—S11i 2.442 (5)Ag6—S2 2.539(4) Ag17—O12 2.482(9)

Ag6—Ag8ii 2.9399(15) Ag17—S6 2.535(6)Ag6—Ag7 3.1581(17) Ag17—S7 2.607 (5)Ag7—O4 2.417(11) Ag18—O13 2.395 (9)Ag7—S6i 2.439(5) Ag18—S7 2.441(4)Ag7—S2 2.477(4) Ag18—S5 2.464(4)

Ag7—Ag12 3.1003(19) Ag19—O13i 2.338(9)Ag8—O6ii 2.446(10) Ag19—S5 2.463(3)Ag8—S2ii 2.456(3) Ag19—O9 2.508 (9)Ag8—S10 2.557(3) Ag19—S8 2.588(3)

Ag8—Ag10 3.1896(17) Ag19—Ag20 2.9911(15)Ag9—O7 2.399(13) Ag20—O3 2.348(12)Ag9—S3 2.466(4) Ag20—S4 2.484(4)Ag9—S2 2.525(4) Ag20—S5i 2.521(4)

Ag9—Ag10 3.2180(16) Ag20—S5 2.897(4)Ag9—Ag11 3.2972(17) Ag20—Ag20i 3.121(2)Ag10—S3 2.429(4) Ag13—O10 2.675 (2)

Ag15—O10 2.518 (5) Ag7—O11 2.619 (3)S12i—Ag1—S12 19.4(15) S4—Ag11—O11i 99.0(3)S14—Ag1—S12 168.0(4) S3—Ag11—O11i 101.4(2)O8—Ag2—S13 110.7(3) S4—Ag11—S8 103.37(13)O8—Ag2—S12i 84.4(6) S3—Ag11—S8 97.38(11)S13—Ag2—S12i 132.7(5) O11i—Ag11—S8 91.0(2)

O8—Ag2—S9 93.4(3) S4—Ag12—S6i 174.25(16)S13—Ag2—S9 124.4(2) S10—Ag13—S8 173.37(13)

S12

S12i—Ag2—S9 97.6(6) S13—Ag14—S10 164.79(14)S14—Ag3—S7i 153.2(4) S9—Ag15—S8 171.35(13)S11—Ag4—S13 158.34(15) S9—Ag15—O10i 98.8(3)S11—Ag4—O5 106.6(3) S8—Ag15—O10i 80.8(3)S13—Ag4—O5 94.8(3) S7—Ag16—S9 169.43(18)S1—Ag5—S11 177.07(17) S11i—Ag17—O12 94.6(3)S1—Ag5—O4 98.0(3) S11i—Ag17—S6 130.23(18)S11—Ag5—O4 82.6(3) O12—Ag17—S6 91.9(3)O2—Ag6—S1 120.2(8) S11i—Ag17—S7 133.60(18)O2—Ag6—S2 104.6(8) O12—Ag17—S7 82.0(3)S1—Ag6—S2 134.98(12) S6—Ag17—S7 96.18(17)O4—Ag7—S6i 120.8(3) O13—Ag18—S7 109.1(2)O4—Ag7—S2 84.5(3) O13—Ag18—S5 103.5(2)S6i—Ag7—S2 149.61(16) S7—Ag18—S5 144.79(16)

O7—Ag8—O6ii 83.3(4) O13i—Ag19—S5 139.5(2)O7—Ag8—S2ii 139.3(3) O13i—Ag19—O9 82.9(3)O6ii—Ag8—S2ii 100.0(2) S5—Ag19—O9 94.8(2)O7—Ag8—S10 77.7(2) O13i—Ag19—S8 96.2(2)O6ii—Ag8—S10 109.5(2) S5—Ag19—S8 123.64(11)S2ii—Ag8—S10 135.84(12) O9—Ag19—S8 101.5(2)O7—Ag9—S3 123.4(2) O3—Ag20—S4 104.6(3)O7—Ag9—S2 100.9(2) O3—Ag20—S5i 112.6(4)S3—Ag9—S2 134.72(13) S4—Ag20—S5i 126.88(16)

S3—Ag10—S1ii 145.46(14) O3—Ag20—S5 107.7(4)S3—Ag10—S10 113.80(11) S4—Ag20—S5 117.85(14)S1ii—Ag10—S10 100.57(13) S5i—Ag20—S5 85.58(12)S4—Ag11—S3 150.46(13)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+3/2, −y+1/2, −z+1.Compound 3

Ag1—N2 2.134 (14) Ag5—S3iii 2.451 (3)Ag1—S4i 2.662 (2) Ag5—S3 2.451 (3)Ag1—S4 2.662 (2) Ag5—O1iii 2.550 (16)Ag1—S4ii 2.662 (2) Ag5—O1 2.550 (16)Ag1—Ag2i 3.2890 (10) Ag5—Ag4iii 3.1155 (9)Ag1—Ag2ii 3.2890 (10) Ag6—S2i 2.395 (3)Ag1—Ag2 3.2890 (10) Ag6—S5 2.397 (3)Ag2—S3 2.482 (3) Ag6—Ag3i 3.0233 (11)Ag2—S4 2.567 (2) Ag6—Ag7 3.2383 (14)Ag2—S4ii 2.574 (2) Ag7—S1i 2.456 (4)Ag2—Ag3 3.0188 (12) Ag7—S1 2.463 (4)Ag2—Ag4 3.0404 (11) Ag7—S5 2.863 (4)Ag3—S2 2.380 (2) Ag7—Ag7i 2.9703 (19)Ag3—S4ii 2.399 (2) Ag7—Ag7ii 2.9703 (19)

S13

Ag3—Ag6ii 3.0233 (11) Ag7—Ag8 3.0461 (17)Ag4—S5 2.384 (3) Ag8—N2 2.113 (11)Ag4—S3 2.402 (3) Ag8—S2 2.566 (3)

Ag4—Ag5 3.1155 (9) Ag8—S5 2.583 (3)Ag4—Ag6 3.2121 (12) Ag8—S1 2.671 (4)

N2—Ag1—S4i 120.16 (5) S3iii—Ag5—O1 109.0 (4)N2—Ag1—S4 120.16 (5) S3—Ag5—O1 96.8 (4)S4i—Ag1—S4 96.97 (6) O1iii—Ag5—O1 52.3 (7)S4i—Ag1—S4ii 96.97 (6) S2i—Ag6—S5 166.64 (11)S4—Ag1—S4ii 96.97 (6) S1i—Ag7—S1 148.06 (17)S3—Ag2—S4 122.30 (9) S1i—Ag7—S5 101.90 (12)S3—Ag2—S4ii 133.46 (9) S1—Ag7—S5 108.26 (12)S4—Ag2—S4ii 101.69 (10) N2—Ag8—S2 118.0 (3)S2—Ag3—S4ii 175.04 (9) N2—Ag8—S5 119.7 (4)S5—Ag4—S3 167.10 (10) S2—Ag8—S5 97.08 (9)

S3iii—Ag5—S3 151.34 (14) N2—Ag8—S1 108.1 (4)S3iii—Ag5—O1iii 96.8 (4) S2—Ag8—S1 101.60 (11)S3—Ag5—O1iii 109.0 (4) S5—Ag8—S1 110.68 (12)

Symmetry codes: (i) −y+1, x−y+1, z; (ii) −x+y, −x+1, z; (iii) −x+4/3, −x+y+2/3, −z+7/6.Compound 4-P62

Ag1—S5 2.457 (2) Ag5—S5 2.550 (2)Ag1—S1 2.483 (2) Ag5—O15 2.595 (7)Ag1—O3 2.495 (6) Ag5—Ag11 2.9789 (10)Ag1—O1i 2.531 (6) Ag5—Ag6 3.0660 (11)Ag1—Ag2 2.9295 (10) Ag5—Ag7 3.0888 (10)Ag1—Ag9 3.0810 (8) Ag6—O10 2.334 (7)Ag1—Ag6 3.0830 (10) Ag6—S2 2.452 (2)Ag2—O11 2.373 (7) Ag6—S5 2.459 (2)Ag2—O12 2.374 (8) Ag6—Ag11 3.0376 (11)Ag2—S2 2.595 (2) Ag7—S3 2.414 (3)Ag2—S1 2.608 (2) Ag7—S5 2.419 (2)

Ag2—Ag6 2.9151 (10) Ag7—O5 2.438 (7)Ag2—Ag8 3.0726 (10) Ag7—O1i 2.577 (6)Ag2—Ag3 3.0866 (11) Ag7—Ag8i 3.3053 (11)Ag3—S2 2.406 (2) Ag8—O9i 2.374 (7)Ag3—S3i 2.409 (3) Ag8—S3i 2.440 (3)Ag3—O2 2.484 (7) Ag8—S1 2.472 (2)Ag3—Ag8 3.1570 (11) Ag8—Ag7i 3.3053 (11)Ag3—Ag4i 3.1575 (10) Ag9—S1 2.458 (2)Ag4—O13 2.379 (7) Ag9—S1i 2.458 (2)Ag4—S4i 2.480 (2) Ag9—Ag1i 3.0810 (8)Ag4—O8ii 2.511 (7) Ag10—S4i 2.484 (2)Ag4—S3 2.553 (3) Ag10—S4 2.484 (2)

S14

Ag4—Ag5 2.9528 (10) Ag10—Ag11 3.2894 (8)Ag4—Ag7 2.9814 (10) Ag10—Ag11i 3.2894 (8)Ag4—Ag3i 3.1575 (10) Ag11—S4i 2.444 (2)Ag5—O14 2.341 (7) Ag11—S2 2.463 (2)Ag5—S4i 2.549 (2) Ag11—O4iii 2.470 (7)

S5—Ag1—S1 164.39 (8) O14—Ag5—S5 104.87 (19)S5—Ag1—O3 103.32 (16) S4i—Ag5—S5 135.21 (8)S1—Ag1—O3 92.16 (15) O14—Ag5—O15 89.3 (2)S5—Ag1—O1i 83.47 (16) S4i—Ag5—O15 120.63 (16)S1—Ag1—O1i 93.07 (15) S5—Ag5—O15 84.27 (16)O3—Ag1—O1i 95.8 (2) O10—Ag6—S2 111.6 (2)

O11—Ag2—O12 87.0 (3) O10—Ag6—S5 98.7 (2)O11—Ag2—S2 105.30 (19) S2—Ag6—S5 144.23 (8)O12—Ag2—S2 105.8 (2) S3—Ag7—S5 166.48 (9)O11—Ag2—S1 110.00 (19) S3—Ag7—O5 98.78 (18)O12—Ag2—S1 95.9 (2) S5—Ag7—O5 94.54 (18)S2—Ag2—S1 139.26 (8) S3—Ag7—O1i 95.44 (16)S2—Ag3—S3i 161.64 (9) S5—Ag7—O1i 83.27 (16)S2—Ag3—O2 84.48 (17) O5—Ag7—O1i 104.9 (2)S3i—Ag3—O2 103.35 (17) O9i—Ag8—S3i 113.1 (2)O13—Ag4—S4i 111.5 (2) O9i—Ag8—S1 104.3 (2)O13—Ag4—O8ii 101.5 (2) S3i—Ag8—S1 142.43 (8)S4i—Ag4—O8ii 106.82 (18) S1—Ag9—S1i 179.88 (12)O13—Ag4—S3 92.3 (2) S4i—Ag10—S4 174.35 (12)S4i—Ag4—S3 148.62 (8) S4i—Ag11—S2 157.68 (8)O8ii—Ag4—S3 87.06 (18) S4i—Ag11—O4iii 110.13 (17)O14—Ag5—S4i 111.45 (19) S2—Ag11—O4iii 91.62 (18)

Symmetry codes: (i) −x+2, −y+1, z; (ii) −y+2, x−y, z−1/3; (iii) y, −x+y+1, z−1/3.Compound 4-P64

Ag1—S5i 2.4549 (14) Ag5—O15 2.589 (4)Ag1—S1 2.4885 (14) Ag5—Ag11 2.9774 (6)Ag1—O3 2.490 (4) Ag5—Ag6 3.0745 (6)Ag1—O1 2.531 (4) Ag5—Ag7 3.0883 (6)Ag1—Ag2 2.9330 (6) Ag6—O10i 2.324 (4)Ag1—Ag6i 3.0798 (6) Ag6—S2i 2.4500 (14)Ag1—Ag9 3.0854 (4) Ag6—S5 2.4579 (14)Ag2—O12 2.374 (5) Ag6—Ag2i 2.9198 (6)Ag2—O11 2.390 (4) Ag6—Ag11 3.0439 (6)Ag2—S2 2.5930 (15) Ag6—Ag1i 3.0798 (6)Ag2—S1 2.6122 (14) Ag7—S3 2.4128 (15)

Ag2—Ag6i 2.9198 (6) Ag7—S5 2.4216 (14)Ag2—Ag8 3.0743 (6) Ag7—O5i 2.443 (4)Ag2—Ag3 3.0841 (6) Ag7—O1i 2.573 (4)

S15

Ag3—S2 2.4099 (14) Ag7—Ag8 3.3043 (6)Ag3—S3 2.4139 (15) Ag8—O9i 2.379 (4)Ag3—O2 2.480 (4) Ag8—S3 2.4405 (15)Ag3—Ag8 3.1566 (6) Ag8—S1 2.4686 (14)Ag3—Ag4 3.1626 (6) Ag9—S1i 2.4584 (13)Ag4—O13 2.379 (4) Ag9—S1 2.4584 (13)Ag4—S4 2.4749 (14) Ag9—Ag1i 3.0854 (5)

Ag4—O8ii 2.515 (4) Ag10—S4 2.4902 (14)Ag4—S3 2.5521 (15) Ag10—S4i 2.4902 (14)

Ag4—Ag5 2.9568 (6) Ag10—Ag11 3.2991 (5)Ag4—Ag7 2.9831 (6) Ag10—Ag11i 3.2991 (5)Ag5—O14 2.344 (4) Ag11—S4 2.4473 (14)Ag5—S4 2.5461 (14) Ag11—O4iii 2.459 (4)Ag5—S5 2.5538 (15) Ag11—S2i 2.4629 (15)

S5i—Ag1—S1 164.49 (5) O14—Ag5—S5 104.70 (11)S5i—Ag1—O3 103.45 (10) S4—Ag5—S5 135.16 (5)S1—Ag1—O3 91.92 (9) O14—Ag5—O15 89.92 (14)S5i—Ag1—O1 83.54 (9) S4—Ag5—O15 120.79 (10)S1—Ag1—O1 92.98 (9) S5—Ag5—O15 84.00 (10)O3—Ag1—O1 95.76 (13) O10i—Ag6—S2i 111.90 (12)

O12—Ag2—O11 86.85 (17) O10i—Ag6—S5 98.91 (12)O12—Ag2—S2 106.40 (13) S2i—Ag6—S5 143.97 (5)O11—Ag2—S2 105.26 (11) S3—Ag7—S5 166.59 (5)O12—Ag2—S1 95.62 (13) S3—Ag7—O5i 99.19 (11)O11—Ag2—S1 110.01 (11) S5—Ag7—O5i 94.01 (11)S2—Ag2—S1 139.14 (5) S3—Ag7—O1i 95.46 (9)S2—Ag3—S3 161.72 (5) S5—Ag7—O1i 83.31 (9)S2—Ag3—O2 84.67 (10) O5i—Ag7—O1i 104.94 (13)S3—Ag3—O2 103.10 (10) O9i—Ag8—S3 113.23 (12)O13—Ag4—S4 111.21 (11) O9i—Ag8—S1 104.08 (12)

O13—Ag4—O8ii 101.52 (14) S3—Ag8—S1 142.54 (5)S4—Ag4—O8ii 107.16 (10) S1i—Ag9—S1 179.96 (7)O13—Ag4—S3 92.42 (12) S4—Ag10—S4i 174.11 (7)S4—Ag4—S3 148.66 (5) S4—Ag11—O4iii 109.72 (11)

O8ii—Ag4—S3 86.90 (10) S4—Ag11—S2i 157.60 (5)O14—Ag5—S4 111.42 (11) O4iii—Ag11—S2i 92.08 (11)

Symmetry codes: (i) −x+1, −y+1, z; (ii) x−y, x, z−1/3; (iii) −x+y+1, −x+1, z−1/3.

S16

Table S2: Crystal data for 1-4

Compound 1 2 3 4

Empirical

formula

C288H340Ag47Cr4

F54N4O56S24

C114H240Ag40C

r5F9O26S27

C124H270Ag41C

r2N7O17S30

C50H98Ag20Cr5

F12N4O30S10

C50H98Ag20Cr5

F12N4O30S10

Formula weight 11826.97 7638.47 7619.94 4201.32 4201.32

Temperature/K 100(2) 173(2) 173(2) 173(2) 173(2)

Crystal system orthorhombic monoclinic trigonal hexagonal hexagonal

Space group Fddd C2/c R-3c P62 P64

a/Å 47.992(3) 32.9630(4) 22.6491(3) 17.5994(5) 17.6030(3)

b/Å 50.873(3) 28.7840(4) 22.6491(3) 17.5994(5) 17.6030(3)

c/Å 64.857(4) 21.7978(3) 71.0014(13) 29.2422(9) 29.2412(5)

α/° 90.00 90.00 90.00 90.00 90.00

β/° 90.00 96.6012(12) 90.00 90.00 90.00

γ/° 90.00 90.00 120.00 120.00 120.00

Volume/Å3 158350(16) 20544.8(5) 31542.7(7) 7844.0(4) 7846.9(2)

Z 16 4 6 3 3

ρcalc g/cm3 1.984 2.471 2.407 2.668 2.667

μ/mm-1 2.577 34.880 4.157 4.426 4.424

F(000) 91504.0 14580.0 21924.0 5982.0 5982.0

Radiation MoKα

(λ=0.71073)

CuKα

(λ=1.54184)

MoKα

(λ=0.71073)

MoKα

(λ = 0.71073)

MoKα

(λ = 0.71073)

2Θ range for data

collection/°

4.1 to 50 6 to 140.16 5.52 to 50 4.96 to 55.02 3.02 to 52

Index ranges -57 ≤ h ≤ 32,

-53 ≤ k ≤ 60,

-71 ≤ l ≤ 77

-39 ≤ h ≤ 39,

-28 ≤ k ≤ 35,

-26 ≤ l ≤ 26

-26 ≤ h ≤ 26,

-26 ≤ k ≤ 26,

-51 ≤ l ≤ 84

-17 ≤ h ≤ 21,

-22 ≤ k ≤ 18,

-28 ≤ l ≤ 37

-21 ≤ h ≤ 17,

-18 ≤ k ≤ 21,

-36 ≤ l ≤ 30

Reflections

collected

153164 38362 29786 29051 47425

Independent

reflections

34435

[Rint=0.133]

19147

[Rint=0.0647]

6177

[Rint=0.0184]

10170

[Rint = 0.0444]

9278

[Rint = 0.0322]

Data/parameters 34435/2313 19147/1144 6177/269 10170/606 9278/606

Goodness-of-fit

on F2

1.084 1.023 1.024 1.102 1.025

Final R indexes

[I>=2σ (I)]

R1= 0.1270,

wR2=0.2998

R1= 0.0717,

wR2= 0.1899

R1= 0.0595,

wR2= 0.1638

R1= 0.0430,

wR2= 0.0621

R1=0.0260,

wR2= 0.0404

Final R indexes

[all data]

R1= 0.2392,

wR2= 0.4122

R1= 0.1091,

wR2= 0.2231

R1= 0.0663,

wR2= 0.1720

R1 =0.0635,

wR2 = 0.0689

R1=0.0316,

wR2= 0.0417

S17

Fig. S1: Four CrO42- ions coordinated to the superadamantane.

S18

Fig. S2: The Ag···π interaction in 1.

S19

Table S3: Calculation result by TOPOS software for 3.

###############################1:C124 H270 Ag41 Cr2 N7 O17 S30###############################

Topology for Sc1 (Sc1=Ag19 cluster)--------------------Atom Sc1 links by bridge ligands and hasCommon vertex with R(A-A) fSc 1 0.0000 0.0000 0.6110 (-1-1 0) 13.655A 1Sc 1 1.0000 1.0000 0.6110 ( 0 0 0) 13.655A 1Sc 1 0.0000 1.0000 0.6110 (-1 0 0) 13.655A 1Sc 1 0.6667 0.3333 0.4444 ( 1 1 1) 15.277A 1Sc 1 -0.3333 0.3333 0.4444 ( 0 1 1) 15.277A 1Sc 1 0.6667 1.3333 0.4444 ( 1 2 1) 15.277A 1Sc 1 0.3333 0.6667 0.7777 ( 0 0 1) 15.767A 1-------------------------Structural group analysis-------------------------

-------------------------Structural group No 1-------------------------Structure consists of 3D framework with Ag3Ti4Sc2

Coordination sequences----------------------Sc1: 1 2 3 4 5 6 7 8 9 10Num 7 24 52 92 143 206 280 366 463 572Cum 8 32 84 176 319 525 805 1171 1634 2206----------------------TD10=2206

Vertex symbols for selected sublattice--------------------------------------Sc1 Point symbol:{4^15.6^6}Extended point symbol:[4.4.4.4.4.4.4(2).4(2).4(2).4(2).4(2).4(2).4(2).4(2).4(2).6(11).6(11).6(11).6(15).6(15).6(15)]--------------------------------------Point symbol for net: {4^15.6^6}7-c net; uninodal net

ATTENTION! If the name below is written in a long notation s/... or s-d-G-n, this net is a subnet of

S20

the net s (see Manual for details)Topological type: kwh; bcu-7-R-3m (uninodal.ttd) {4^15.6^6} - VS [4.4.4.4.4.4.4(2).4(2).4(2).4(2).4(2).4(2).4(2).4(2).4(2).6(3).6(3).6(3).6(7).6(7).6(7)] (72442 types in 11 databases)

-----------------------Non-equivalent circuits-----------------------Circuit No 1; Type=4a; Centroid: (0.500,0.500,0.625)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 1.0000 1.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 0.0000 0.0000 0.6110

Circuit No 2; Type=4b; Centroid: (0.250,0.250,0.500)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 0.0000 0.0000 0.3890Sc1 0.0000 0.0000 0.6110

Circuit No 3; Type=6a; Centroid: (0.444,0.556,0.472)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.0000 -0.0000 0.3890Sc1 0.6667 0.3333 0.4444Sc1 1.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 4; Type=6b; Centroid: (0.500,0.500,0.500)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 0.3333 -0.3333 0.5556

S21

Sc1 0.6667 0.3333 0.4444Sc1 1.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 5; Type=6c; Centroid: (0.667,0.833,0.583)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 1.0000 1.0000 0.6110Sc1 1.3333 1.6667 0.5556Sc1 0.6667 1.3333 0.4444

Circuit No 6; Type=6d; Centroid: (0.611,0.722,0.556)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 1.0000 1.0000 0.6110Sc1 1.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 7; Type=6e; Centroid: (0.111,0.556,0.472)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.0000 -0.0000 0.3890Sc1 -0.3333 0.3333 0.4444Sc1 0.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 8; Type=6f; Centroid: (0.000,0.500,0.500)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.6667 -0.3333 0.5556

S22

Sc1 -0.3333 0.3333 0.4444Sc1 0.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 9; Type=6g; Centroid: (0.333,0.667,0.417)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.0000 -0.0000 0.3890Sc1 0.3333 0.6667 0.2777Sc1 0.6667 1.3333 0.2223Sc1 0.6667 1.3333 0.4444

Circuit No 10; Type=6h; Centroid: (0.389,0.611,0.444)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.0000 -0.0000 0.3890Sc1 0.3333 0.6667 0.2777Sc1 1.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 11; Type=6i; Centroid: (0.222,0.611,0.444)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.0000 -0.0000 0.3890Sc1 0.3333 0.6667 0.2777Sc1 0.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 12; Type=6j; Centroid: (0.111,0.722,0.556)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.0000 0.0000 0.6110Sc1 -0.3333 0.3333 0.7223

S23

Sc1 -0.0000 1.0000 0.6110Sc1 0.0000 1.0000 0.3890Sc1 0.6667 1.3333 0.4444

Circuit No 13; Type=6k; Centroid: (0.833,0.667,0.667)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 1.3333 0.6667 0.5556Sc1 1.3333 0.6667 0.7777Sc1 1.0000 1.0000 0.8890Sc1 0.3333 0.6667 0.7777Crossed with bonds------------------------------------------------------------------------------------------------ No | Atom x y z | Atom x y z | Dist. | N Cycles------------------------------------------------------------------------------------------------* 2 | Sc1 1.0000 1.0000 0.6110 | Sc1 0.6667 0.3333 0.7223 | 15.277 | 6k/1 6k/1 6k/1 6k/1 ------------------------------------------------------------------------------------------------

Circuit No 14; Type=6l; Centroid: (0.778,0.556,0.639)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 1.3333 0.6667 0.5556Sc1 1.3333 0.6667 0.7777Sc1 0.6667 0.3333 0.7223Sc1 0.3333 0.6667 0.7777

Circuit No 15; Type=6m; Centroid: (0.667,0.833,0.583)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 1.0000 1.0000 0.3890Sc1 1.0000 1.0000 0.6110Sc1 0.6667 1.3333 0.7223Sc1 0.3333 0.6667 0.7777

S24

Circuit No 16; Type=6n; Centroid: (0.722,0.611,0.611)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 1.3333 0.6667 0.5556Sc1 1.0000 1.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 0.3333 0.6667 0.7777

Circuit No 17; Type=6o; Centroid: (0.667,0.667,0.583)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 1.0000 1.0000 0.3890Sc1 1.0000 1.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 0.3333 0.6667 0.7777

Circuit No 18; Type=6p; Centroid: (0.389,0.278,0.611)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 0.3333 -0.3333 0.5556Sc1 0.0000 0.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 0.3333 0.6667 0.7777

Circuit No 19; Type=6q; Centroid: (0.333,0.333,0.583)------------------------------Atom x y z------------------------------Sc1 0.3333 0.6667 0.5556Sc1 0.6667 0.3333 0.4444Sc1 0.0000 0.0000 0.3890Sc1 0.0000 0.0000 0.6110Sc1 0.6667 0.3333 0.7223Sc1 0.3333 0.6667 0.7777

S25

Ring links------------------------------------------------------Cycle 1 | Cycle 2 | Chain | Cross | Link | Hopf | Mult------------------------------------------------------ 6k | 6k | 1 | 1 | 1 | * | 4------------------------------------------------------

Elapsed time: 10.00 sec.

S26

Table S4: Calculation result by TOPOS software for 4.

#################################1:C50 H98 Ag20 Cr5 F12 N4 O30 S10#################################

Topology for Sc1 (Sc1=Ag20 cluster)--------------------Atom Sc1 links by bridge ligands and hasCommon vertex with R(A-A) fSc 1 0.5000 1.0000 0.6129 ( 0 1 0) 13.132A 1Sc 1 -0.5000 0.0000 0.6129 (-1 0 0) 13.132A 1Sc 1 -0.5000 0.5000 -0.0538 ( 0 1-1) 13.132A 1Sc 1 0.5000 0.5000 -0.0538 ( 1 1-1) 13.132A 1-------------------------Structural group analysis-------------------------

-------------------------Structural group No 1-------------------------Structure consists of 3D framework with Ti2Sc

Coordination sequences----------------------Sc1: 1 2 3 4 5 6 7 8 9 10Num 4 12 30 52 80 116 156 204 258 318Cum 5 17 47 99 179 295 451 655 913 1231----------------------TD10=1231

Vertex symbols for selected sublattice--------------------------------------Sc1 Point symbol:{6^4.8^2}Extended point symbol:[6.6.6(2).6(2).8(9).8(9)]--------------------------------------Point symbol for net: {6^4.8^2}4-c net; uninodal net

Topological type: qtz Quartz; 4/6/h1 (topos&RCSR.ttd) {6^4.8^2} - VS [6.6.6(2).6(2).8(7).8(7)] (72442 types in 11 databases)----------------------------------------------Minimum circuits for independent edges (bonds)----------------------------------------------------------------------------------------

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No | Atom x y z | Atom x y z | Dist. | N---------------------------------------------------------------------------------------- 1 | Sc1 0.0000 0.5000 0.2795 | Sc1 0.5000 0.5000 -0.0538 | 13.132 | 6----------------------------------------------------------------------------------------

-----------------------Non-equivalent circuits-----------------------Circuit No 1; Type=6a; Centroid: (0.000,0.500,0.780)------------------------------Atom x y z------------------------------Sc1 0.0000 0.5000 0.2795Sc1 0.5000 1.0000 0.6129Sc1 0.5000 0.5000 0.9462Sc1 0.0000 0.5000 1.2795Sc1 -0.5000 0.5000 0.9462Sc1 -0.5000 -0.0000 0.6129

Circuit No 2; Type=8a; Centroid: (0.000,0.188,0.280)------------------------------Atom x y z------------------------------Sc1 0.0000 0.5000 0.2795Sc1 -0.5000 0.5000 -0.0538Sc1 -0.5000 -0.0000 -0.3871Sc1 -0.5000 -0.5000 -0.0538Sc1 0.0000 -0.5000 0.2795Sc1 0.5000 0.0000 0.6129Sc1 0.5000 0.5000 0.9462Sc1 0.5000 1.0000 0.6129

Circuit No 3; Type=8b; Centroid: (0.813,0.625,0.613)------------------------------Atom x y z------------------------------Sc1 1.0000 0.5000 0.2795Sc1 0.5000 0.5000 -0.0538Sc1 0.0000 0.5000 0.2795Sc1 0.5000 1.0000 0.6129Sc1 0.5000 0.5000 0.9462Sc1 1.0000 0.5000 1.2795Sc1 1.5000 0.5000 0.9462

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Sc1 1.5000 1.0000 0.6129

Circuit No 4; Type=8c; Centroid: (0.938,0.063,0.446)------------------------------Atom x y z------------------------------Sc1 1.0000 -0.5000 0.2795Sc1 0.5000 -0.5000 -0.0538Sc1 0.0000 -0.5000 0.2795Sc1 0.5000 0.0000 0.6129Sc1 1.0000 0.5000 0.2795Sc1 1.5000 1.0000 0.6129Sc1 1.5000 0.5000 0.9462Sc1 1.5000 0.0000 0.6129

Circuit No 5; Type=8d; Centroid: (0.000,0.000,0.280)------------------------------Atom x y z------------------------------Sc1 0.0000 -0.5000 0.2795Sc1 -0.5000 -0.5000 -0.0538Sc1 -1.0000 -0.5000 0.2795Sc1 -0.5000 -0.0000 0.6129Sc1 0.0000 0.5000 0.2795Sc1 0.5000 0.5000 -0.0538Sc1 1.0000 0.5000 0.2795Sc1 0.5000 0.0000 0.6129

Elapsed time: 6.11 sec.

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Fig. S3: The coordination mode of Cr2O72- in 4.

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Fig. S4: Comparison of the experimental (red) and simulated (black) spectra of isotopic envelope for species 1a-1e recorded during ESI-MS analyses of a reaction solution of 1.

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Fig. S5: Comparison of the experimental (red) and simulated (black) spectra of isotopic envelope for species 2a-2f recorded during ESI-MS analyses of a reaction solution of 2.

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Fig. S6: Comparison of the experimental (red) and simulated (black) spectra of isotopic envelope for species 3a-3o recorded during ESI-MS analyses of a reaction solution of 3.

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Fig. S7: The TGA of 1-3.

100 200 300 400 500 600 700 800 90040

50

60

70

80

90

100

TG (%

)

Temperature (C)

1 2 3

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Fig. S8: The cyclic voltammograms of 1-, 2-, 3-CPEs in 1 M H2SO4 solution at a

scan rate 0.04 V s-1.

Fig. S9: Cyclic voltammogram of the precursor {(HNEt3)2[Ag10(tBuC6H4S)12]}n in

1 M H2SO4 aqueous solution.

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Fig. S10: Cyclic voltammogram of the precursor [AgiBuS]n in 1 M H2SO4 aqueous

solution.

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Fig. S11: The cyclic voltammograms of bare CPE, and 1, 2, 3-CPEs in 1 M H2SO4

solution in the absence and presence of 0.1 M H2O2 (scan rate: 0.05 V s-1).

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Fig. S12: The compared solid-state UV-Vis spectra of 3 when doped with I2 in an

amount from 5 to 30 wt%. The lower plot is solid-state UV-Vis spectrum of

iodine.

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Fig. S13: The compared electron paramagnetic resonance spectra of 3 with doped

the I2 amount from 0 to 30 wt%.

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Fig. S14: The compared IR spectra of 1-3.

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Fig. S15: Compared I-V curves with different iodine weight fraction for 1-3.

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Fig. S16: Microscope photographs of crystals 2 and 3 and the powder samples of 1-3.

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Fig. S17: The IR spectrum of 4.