Table S1. Summary of data collections and structure refinements for crystals 1Rb-1h, 1Rb-2h, and 1Rb-4h.

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1 Supporting Information [NH 3 CH 3 ] [In SbS 9 SH]: A novel methylamine-directed indium thioantimonate with Rb + ion-exchange property Kai-Yao Wang a,b, Mei-Ling Feng a, Jian-Rong Li a and Xiao-Ying Huang *,a a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, the Chinese, Academy of Sciences, Fuzhou, Fujian , P.R. China b Graduate University of the Chinese Academy of Sciences, Beijing 10009, P. R. China Fax: ; Tel: ; xyhuang@fjirsm.ac.cn Table S1. Summary of data collections and structure refinements for crystals 1Rb-1h, 1Rb-2h, and 1Rb-h. 1Rb 1h 1Rb 2h 1Rb h Empirical formula Formula weight Crystal system Space group T/K λ/å a/å b/å c/å α/º β/º γ/º V/Å 3 Z D c /Mg m -3 μ/mm -1 F(000) Measured refls. Independent refls. C 3.6 H 22.8 In N 3.6 O 0.1 Rb 0. S 10 Sb () () () (13) C 3.2 H 20.6 In N 3.2 O 0.2 Rb 0.8 S 10 Sb (8) (8) (8) (3) C 2.75 H In N 2.75 O Rb 1.25 S 10 Sb (13) (13) (13) () R int No. of parameters GOF Flack parameter a R 1, wr 2 [I > 2 (I)] R 1, wr 2 (all data) (11) 0.022, , (12) , , (11) , , 0.16 a R 1 = Fo - Fc / Fo, wr 2 = { w[(fo) 2 -(Fc) 2 ] 2 / w[(fo) 2 ] 2 } 1/2.

2 Table S2. Summary of data collections and structure refinements for crystals 1Rb-6h, 1Rb-12h 1Rb-8h and 1Cs-36h. 1Rb 6h 1Rb 12h 1Rb 8h 1Cs-36h Empirical formula C 2 H 1 In N 2 O 0.50 Rb 2 S 10 Sb C 1.3 H In N 1.3 O Rb 2.7 S 10 Sb C 0.7 H 6.85 In N 0.7 O Rb 3.3 S 10 Sb C 3.71 H In N 3.71 Cs 0.29 S 10 Sb Formula weight Crystal system Space group T/K λ/å a/å b/å c/å α/º β/º γ/º V/Å 3 Z D c /Mg m -3 μ/mm -1 F(000) Measured refls. Independent refls. Peak and hole/e Å (13) (13) (13) () / (3) (3) (3) (10) / (2) (2) (2) (8) / (1) 13.56(1) 13.56(1) (3) / R int No. of parameters GOF Flack parameter a R 1, wr 2 [I > 2 (I)] R 1, wr 2 (all data) (9) 0.065, , (5) , , (2) , , (9) 0.009, , a R 1 = Fo - Fc / Fo, wr 2 = { w[(fo) 2 -(Fc) 2 ] 2 / w[(fo) 2 ] 2 } 1/2. Table S3. Selected bond lengths (Å) and angles ( ) for compounds 1 and 1Rb-2h. 1 1Rb-2h In(1)-S(2)#1 2.62(19) In(1)-S(2)#1 2.28(3) In(1)-S(2) 2.62(19) In(1)-S(2) 2.28(3) In(1)-S(2)#2 2.62(19) In(1)-S(2)#2 2.28(3) In(1)-S(1) 2.76() In(1)-S(1) 2.27(7) In(2)-S() 2.35(19) In(2)-S() 2.25(3) In(2)-S(2) 2.52(19) In(2)-S(2) 2.3(3) In(2)-S()# (18) In(2)-S()#1 2.0(3) In(2)-S(3) 2.75(17) In(2)-S(3) 2.71(3)

3 Sb(1)-S(3) 2.35(18) Sb(1)-S(3) 2.31(3) Sb(1)-S(3)#3 2.35(18) Sb(1)-S(3)# 2.31(3) Sb(1)-S(3)# 2.35(18) Sb(1)-S(3)#5 2.31(3) S()-In(2)# (18) S()-In(2)#2 2.0(3) S(2)#1-In(1)-S(2) () S(2)#1-In(1)-S(2) (7) S(2)#1-In(1)-S(2)# () S(2)#1-In(1)-S(2)# (7) S(2)-In(1)-S(2)# () S(2)-In(1)-S(2)# (7) S(2)#1-In(1)-S(1) (5) S(1)-In(1)-S(2)# (7) S(2)-In(1)-S(1) (5) S(1)-In(1)-S(2) (7) S(2)#2-In(1)-S(1) (5) S(1)-In(1)-S(2)# (7) S()-In(2)-S(2) 116.3(7) S()-In(2)-S(2) 11.20(10) S()-In(2)-S()# (9) S()-In(2)-S()# (1) S(2)-In(2)-S()# (7) S()#1-In(2)-S(2) (11) S()-In(2)-S(3) (7) S()-In(2)-S(3) (10) S(2)-In(2)-S(3) 106.7(7) S(2)-In(2)-S(3) 10.13(10) S()#1-In(2)-S(3) (6) S()#1-In(2)-S(3) (9) S(3)-Sb(1)-S(3)#3 95.9(6) S(3)-Sb(1)-S(3)# 95.82(9) S(3)-Sb(1)-S(3)# 95.9(6) S(3)-Sb(1)-S(3)# (9) S(3)#3-Sb(1)-S(3)# 95.9(6) S(3)#-Sb(1)-S(3)# (9) In(1)-S(2)-In(2) (7) In(1)-S(2)-In(2) (11) Sb(1)-S(3)-In(2) 99.18(6) Sb(1)-S(3)-In(2) 95.9(9) In(2)-S()-In(2)# (7) In(2)-S()-In(2)# (10) Symmetry transformations used to generate equivalent atoms for 1: #1 y+1/2, -z+1/2, -x+1; #2 -z+1, x-1/2, -y+1/2; #3 z+1/2, -x+3/2, -y+1; # -y+3/2, -z+1, x-1/2; for 1Rb-2h: #1 z, x, y; #2 y, z, x; #3 z+1/2, -x+3/2, -y+1; # -z+1, x+1/2, -y+3/2; #5 y-1/2, -z+3/2, -x+1. Table S. N%, C%, H% analyses and ICP-OES results of the pristine compound 1 and the ion-exchanged products. Exchanged Cations N, C, H analyses Experiment (%) (Calc.) compound ,.88, 2.1 (5.3,.66, 2.) Rb + exchange for 1h.73,.27, 2.22 (.78,.10, 2.18) Rb + exchange for 2h.03, 3.71, 2.01 (.16, 3.57, 1.93) Rb + exchange for h 3.37, 3.12, 1.7 (3.9, 2.99, 1.66) ICP-OES results Estimated formulae Exchange Rb 0.5 In.00 Rb 0.77 In.00 Rb 1.22 In.00 / / Rb 0. (NH 3 CH 3 ) 3.6 In SbS 9 SH 0.1H 2 O Rb 0.8 (NH 3 CH 3 ) 3.2 In SbS 9 SH 0.2H 2 O Rb 1.25 (NH 3 CH 3 ) 2.75 In SbS 9 SH H 2 O yield (%)

4 Rb + exchange for 6h 2.25, 2.21, 1.22 Rb 1.71 In.00 Rb 2 (NH 3 CH 3 ) 2 In SbS 9 SH 50 (2., 2.09, 1.23) 0.5H 2 O Rb + exchange for 12h 1.36, 1.38, 0.88 Rb 2.2 In.00 Rb 2.7 (NH 3 CH 3 ) 1.3 In SbS 9 SH 67.5 (1.53, 1.32, 0.86) 0.675H 2 O Rb + exchange for 2h 0.76, 0.87, 0.3 Rb 3.35 In.00 Rb 3.3 (NH 3 CH 3 ) 0.7 In SbS 9 SH 82.5 (0.80, 0.69, 0.57) 0.825H 2 O Rb + exchange for 36h 0.75, 0.95, 0.57 Rb 3.22 In.00 Rb 3.22 (NH 3 CH 3 ) 0.78 In SbS 9 SH 80.5 (0., 0.77, 0.61) 0.825H 2 O Rb + exchange for 8h 0.7, 0., 0.57 Rb 3.18 In.00 Rb 3.18 (NH 3 CH 3 ) 0.82 In SbS 9 SH 79.5 (0.9, 0.81, 0.63) 0.825H 2 O Na + exchange for 2h 5.0,.55, 1.98 Na 0.20 In.00 Na 0.18 (NH 3 CH 3 ) 3.82 In SbS 9 SH.5 (5.17,.3, 2.0) 0.H 2 O Na + exchange for 36h.,.56, 2.3 Na 0.33 In.00 Na 0.19 (NH 3 CH 3 ) 3.81 In SbS 9 SH.8 (5.11,.38, 2.6) 0.8H 2 O Na + exchange for 8h.76,.37, 2.3 Na 0.32 In.00 Na 0.2 (NH 3 CH 3 ) 3.8 In SbS 9 SH 5.0 (5.10,.37, 2.5) 0.8H 2 O K + exchange for 2h 3.72, 3.50, 1.55 K 1.3 In.00 K 0.95 (NH 3 CH 3 ) 3.05 In SbS 9 SH 23.8 (.07, 3.9, 1.97) 0.6H 2 O K + exchange for 36h 3.68,3.9, 2.03 K 1.31 In.00 K 1.09 (NH 3 CH 3 ) 2.91 In SbS 9 SH 27.3 (3.87, 3.32, 1.92) 0.8H 2 O K + exchange for 8h 3.63, 3.38, 1.99 K 1.23 In.00 K 1.06 (NH 3 CH 3 ) 2.9 In SbS 9 SH 26.5 (3.92, 3.36, 1.92) 0.7H 2 O Cs + exchange for 2h.5,.17, 1.9 weak emission Cs 0.35 (NH 3 CH 3 ) 3.65 In SbS 9 SH 8.8 (.77,.09, 2.21) 0.3H 2 O Cs + exchange for 36h.87,.59, 2.15 weak emission Cs 0.29 (NH 3 CH 3 ) 3.71 In SbS 9 SH 7.3 (.89,.20, 2.23) 0.1H 2 O Cs + exchange for 8h.75,.39, 2.10 weak emission Cs 0.3 (NH 3 CH 3 ) 3.7 In SbS 9 SH 7.5 (.87,.17, 2.23) 0.2H 2 O Rb + + Na , 0.72, 0.61 Na 0.18 Rb 2.61 In.00 Rb 3.11 Na 0.21 (NH 3 CH 3 ) 0.68 In SbS 9 SH Rb + : 77.8 exchange for 2h (0.79, 0.67, 0.56) 0.83H 2 O Na + : 5.2 Rb + + K , 0.73, 0.55 K 0.1 Rb 2.18 In.00 Rb 2.82 K 0.53 (NH 3 CH 3 ) 0.65 In SbS 9 SH Rb + : 70.5 exchange for 2h (0.76, 0.65, 0.55) 0.8H 2 O K + : 13.3 Rb + + Cs +.83,.12, 2.07 Rb 0.11 In.00 Rb 0.11 Cs 0.23 (NH 3 CH 3 ) 3.66 In SbS 9 SH Rb + : 2.8 exchange for 2h (.83,.1, 2.20) 0.09H 2 O Cs + : 5.8 Rb + + Na + + K , 0.7, 0.59 Na 0.01 K 0. Rb 2.68 In.00 Rb 3.03 Na 0.01 K 0.50 (NH 3 CH 3 ) 0.6 In SbS 9 SH Rb + : 75.8 exchange for 2h (0.53,0.6,0.6) 0.885H 2 O Na + : 0.25 K + : 12.5 Rb + + Na + + K + + Cs +.60,.12, 2.1 Na 0.03 K 0.8 Rb 0.10 In.00 Rb 0.06 Na 0.02 K 0.32 Cs 0.13 (NH 3 CH 3 ) 3.7 In SbS 9 SH Rb + : 1.5 exchange for 2h (.62, 3.96, 2.12) 0.13H 2 O Na + : 0.5 K + : 8.0 Cs + : 3.3

5 Figure S1. Thermogravimetric curves for (a) 1 and the 2h Na + -, K + -, Rb + -, Cs + -exchanged products and (b) 1 and the time-dependent Rb + -exchanged products. Figure S2. Thermogravimetric curves for 1 and the time-dependent Rb + -exchanged products in the low-temperature region. Table S5. Thermogravimetric analyses of 1 and the Na + -, K + -, Rb + -, Cs + -exchanged products in 2h. Exchanged cation Estimated formula Experimental weight loss at ~20 3 C (%) Calculated weight loss (%) Pristine \ (2.50 H 2 S+ CH 3 NH 2 ) Na + Na 0.18 (NH 3 CH 3 ) 3.82 In SbS 9 SH 0.H 2 O K + K 0.95 (NH 3 CH 3 ) 3.05 In SbS 9 SH 0.6H 2 O 1.35 Rb + Rb 3.3 (NH 3 CH 3 ) 0.7 In SbS 9 SH 0.825H 2 O (1.91 H 2 S+3.82 CH 3 NH 2 ) 0.61 (H 2 O) (1.53 H 2 S+3.05 CH 3 NH 2 ) 1.03 (H 2 O).15 (0.85 H 2 S+0.7 CH 3 NH 2 ) 1.22 (H 2 O)

6 Cs + Cs 0.35 (NH 3 CH 3 ) 3.65 In SbS 9 SH 0.3H 2 O (1.825 H 2 S+3.65 CH 3 NH 2 ) 0.50 (H 2 O) Table S6. Thermogravimetric analyses of 1 and the time-dependent Rb + -exchanged products. Reaction Estimated formula Experimental Calculated weight losses (%) time weight losses at ~20 3 C (%) 1h Rb 0. (NH 3 CH 3 ) 3.6 In SbS 9 SH 0.1H 2 O h Rb 0.8 (NH 3 CH 3 ) 3.2 In SbS 9 SH 0.2H 2 O h Rb 1.25 (NH 3 CH 3 ) 2.75 In SbS 9 SH H 2 O h Rb 2 (NH 3 CH 3 ) 2 In SbS 9 SH 0.5H 2 O h Rb 2.7 (NH 3 CH 3 ) 1.3 In SbS 9 SH 0.675H 2 O h Rb 3.3 (NH 3 CH 3 ) 0.7 In SbS 9 SH 0.825H 2 O (2.3 H 2 S+3.6 CH 3 NH 2 ) 0.17 (H 2 O) (2.1 H 2 S+3.2 CH 3 NH 2 ) 0.33 (H 2 O) 13.52(1.875 H 2 S+2.75 CH 3 NH 2 ) 0.51 (H 2 O) 9.87 (1.5 H 2 S+2 CH 3 NH 2 ) 0.78 (H 2 O) 6.81 (1.15 H 2 S+1.3 CH 3 NH 2 ) 1.02 (H 2 O).15 (0.85 H 2 S+0.7 CH 3 NH 2 ) 1.22 (H 2 O)