1. Figures
Figure S1. Experimental (top) and simulated (bottom) powder X-ray diffraction patterns of KSb5S8 (1, a), RbSb5S8 (2, b), and CsSb5S8 (3, c).
Figure S2. EDS spectra of 1 (a), 2 (b), and 3 (c).
Figure S3. Powder X-ray diffraction patterns of glassy 1, 2, and 3, showing their amorphous nature.
Figure S4. IR spectra of 1−3.
Figure S5. UV−Vis diffuse-reflectance spectra of 1 (a), 2 (b), and 3 (c).
Figure S6. Electronic band structures of 1 (a), 2 (b), and 3 (c). The Fermi level is set to 0 eV for all band structures.
Figure S7. Total and partial density of states (TDOS and PDOS) of 1 (a), 2 (b), and 3 (c). Figure S8. Calculated frequency dependent SHG coefficients of 1 (a) and 2 (b).
Figure S9. Current−voltage (I−V) plots of 3 and glassy 3.
Figure S10. Asymmetric unit structure of compounds 2 (a) and 3 (b). Alkali metals are omitted for clarity.
2. Tables
Table S1. Fractional atomic coordinates (× 104) and equivalent isotropic displacement parameters
(Å2 × 103) for 1−3. U
eq is defined as 1/3 of the trace of the orthogonalized UIJ tensor. Table S2. Selected interatomic distances (Å) in 1−3.
1. Figures
Figure S1. Experimental (top) and simulated (bottom) powder X-ray diffraction patterns of
Figure S2. EDS spectra of 1 (a), 2 (b), and 3 (c).
Figure S3. Powder X-ray diffraction patterns of glassy 1, 2, and 3, showing their overall
Figure S4. IR spectra of 1−3.
Figure S6. Electronic band structures of 1 (a), 2 (b), and 3 (c). The Fermi level is set to 0 eV for
Figure S8. Calculated frequency dependent SHG coefficients of 1 (a) and 2 (b).
Figure S10. Asymmetric unit structure of compounds 2 (a) and 3 (b). Alkali metals are omitted
2. Tables
Table S1. Fractional atomic coordinates (× 104) and equivalent isotropic displacement parameters
(Å2 × 103) for 1−3. U
eq is defined as 1/3 of the trace of the orthogonalized UIJ tensor.
1 Atom x y z Ueq K1 -215(3) 5510.1(10) 6031(2) 29.7(5) K2 7894(3) -582.4(10) 3416(2) 31.0(5) Sb1 1600.6(7) 2857.2(3) 1000.6(6) 18.57(13) Sb2 -1413.1(8) 3511.9(3) 8079.4(7) 22.06(14) Sb3 5459.9(7) 2115.9(3) 2911.3(6) 17.97(13) Sb4 -1988.6(8) 3719.0(3) 3690.6(6) 17.56(13) Sb5 3656.2(8) -1488.7(3) 735.8(6) 18.26(13) Sb6 3697.3(8) -1275.0(3) 5476.6(6) 18.03(13) Sb7 4879.7(8) 2403.4(3) -1513.8(6) 18.34(13) Sb8 2030.2(8) 2722.8(3) 5429.5(6) 22.97(14) Sb9 4936.5(8) 4539.9(3) 6335.4(6) 19.19(13) Sb10 2643.9(9) 450.8(3) 3879.9(7) 27.17(15) S1 3971(3) 1584.8(10) 5032(2) 17.4(5) S2 160(3) 3905.9(10) 5604(2) 16.9(4) S3 1906(3) -973.6(11) 3390(2) 21.4(5) S4 3320(3) 1778.6(10) 1009(2) 17.2(4) S5 5464(3) -2069.9(11) 2542(2) 20.1(5)
S10 -3396(3) 4827.7(10) 4184(2) 19.8(4) S11 -3014(3) 2761.1(12) 10244(2) 22.6(5) S12 -3534(3) 3026.4(11) 6392(2) 18.8(5) S13 -645(3) 4195.3(10) 1471(2) 21.1(5) S14 6844(3) 989.3(10) 2488(2) 20.4(5) S15 4768(3) -64.6(10) 5531(2) 20.4(5) S16 5300(3) -412.1(12) 556(3) 24.8(5) 2 Atom x y z Ueq Rb1 8886(2) 609.5(7) 5839.0(18) 25.6(4) Rb2 10866(3) 4486.2(10) 8427(2) 53.6(6) Sb1 7624.6(12) 2870.5(5) 8412.9(11) 19.4(2) Sb2 4668.3(12) 1501.7(5) 3129.4(11) 18.9(2) Sb3 11472.8(12) 2126.2(5) 320.1(10) 18.1(2) Sb4 9693.2(13) -1270.4(5) 2868.6(11) 18.4(2) Sb5 14036.0(13) 3725.9(5) 1090.8(11) 19.6(2) Sb6 14589.8(14) 3511.1(5) 5492.9(13) 25.4(3) Sb7 8023.7(13) 2734.8(6) 2825.2(11) 23.8(3) Sb8 10898.2(13) 2416.3(5) 5887.2(11) 18.7(2) Sb9 10970.3(13) 4539.6(5) 3746.8(12) 20.8(2) Sb10 8669.0(15) 465.4(5) 1276.4(13) 28.5(3) S1 13012(5) 2759(2) 7643(4) 23.2(9) S2 9973(5) 1591.2(17) 2433(4) 17.5(8) S3 16164(5) 3905.5(19) 3007(4) 19.6(8) S4 9052(5) 3412.7(18) 6282(4) 20.8(8)
S7 12480(5) 3032.1(19) 3795(4) 18.8(8) S8 9302(5) 3354.8(19) 10387(4) 21.8(8) S9 9338(5) 1800.8(18) 8433(4) 17.6(8) S10 15388(5) 4200.2(18) -1112(4) 21.1(8) S11 6455(5) 2089.8(18) 4926(4) 18.9(8) S12 6302(5) 431.8(18) 2928(5) 23.5(9) S13 13117(5) 4642(2) 5632(5) 28.5(10) S14 12628(5) 4826.4(19) 1597(5) 26.1(9) S15 10738(5) -62.4(18) 2938(4) 19.5(8) S16 12814(5) 1000.3(17) -144(4) 21.0(8) 3 Atom x y z Ueq Cs1 2362.3(2) 8622.5(3) 25.2(2) 33.04(7) Sb1 6220.2(2) 9430.5(3) 2253.3(2) 19.59(7) Sb2 6153.9(2) 5717.0(3) 1160.1(2) 18.21(6) Sb3 3863.7(2) 6104.7(3) 2545.0(2) 17.55(6) Sb4 4022.2(2) 12343.3(3) 1448.1(2) 19.21(7) Sb5 3935.6(2) 9553.3(3) 4011.9(2) 20.72(7) S1 4141.7(8) 9510.1(9) 2202.9(5) 18.97(18) S2 1141.7(9) 8356.9(10) 2133.4(6) 25.6(2) S3 4060.9(7) 5086.1(10) 716.6(5) 17.77(18) S4 5943.0(9) 8418.6(10) 750.8(5) 25.7(2) S5 8993.0(7) 11236.8(9) 2277.4(5) 17.93(18) S6 6140.3(8) 12175.2(10) 1719.2(6) 23.8(2)
Table S2. Selected interatomic distances (Å) in 1−3. 1
Bond Length/Å Bond Length/Å Bond Length/Å
K1–S6 3.126(3) Sb1–S7 2.513(2) Sb6–S15 2.513(2) K1–S7 3.163(3) Sb1–S4 2.524(2) Sb7–S11 2.401(2) K1–S2 3.165(3) Sb2–S12 2.454(2) Sb7–S7 2.504(2) K1–S9 3.227(3) Sb2–S9 2.516(2) Sb7–S12 2.626(2) K1–S10 3.237(3) Sb2–S2 2.727(2) Sb7–S4 2.916(2) K1–S10 3.310(3) Sb2–S11 2.801(2) Sb8–S8 2.432(2) K1–S9 3.441(3) Sb3–S4 2.493(2) Sb8–S5 2.657(2) K1–S13 3.768(4) Sb3–S14 2.502(2) Sb8–S6 2.747(2) K2–S14 3.280(3) Sb3–S1 2.525(2) Sb8–S1 2.752(2) K2–S16 3.299(3) Sb4–S2 2.445(2) Sb8–S2 2.769(2) K2–S4 3.317(3) Sb4–S10 2.492(2) Sb9–S9 2.428(2) K2–S15 3.317(3) Sb4–S13 2.498(2) Sb9–S10 2.475(2) K2–S16 3.328(3) Sb5–S5 2.440(2) Sb9–S13 2.513(2) K2–S3 3.351(3) Sb5–S16 2.495(2) Sb10–S15 2.459(2) K2–S15 3.387(3) Sb5–S8 2.584(2) Sb10–S16 2.477(2) K2–S5 3.580(3) Sb6–S3 2.418(2) Sb10–S1 2.656(2) K2–S1 3.761(3) Sb6–S14 2.466(2) Sb10–S3 2.870(2) Sb1–S6 2.410(2) 2
Bond Length/Å Bond Length/Å Bond Length/Å
Rb1–S9 3.326(4) Sb1–S8 2.416(4) Sb6–S1 2.793(4)
Rb1–S16 3.381(4) Sb2–S12 2.493(4) Sb7–S8 2.759(4) Rb1–S5 3.409(5) Sb2–S6 2.592(4) Sb7–S2 2.777(4) Rb1–S15 3.423(4) Sb3–S9 2.490(4) Sb8–S1 2.409(4) Rb1–S11 3.595(4) Sb3–S16 2.502(3) Sb8–S4 2.498(4) Rb1–S2 3.770(4) Sb3–S2 2.536(4) Sb8–S7 2.625(4) Rb2–S8 3.138(4) Sb4–S5 2.414(4) Sb8–S9 2.934(4) Rb2–S3 3.179(4) Sb4–S16 2.464(4) Sb9–S13 2.421(5) Rb2–S13 3.196(5) Sb4–S15 2.513(4) Sb9–S14 2.476(4) Rb2–S4 3.197(5) Sb5–S3 2.447(4) Sb9–S10 2.515(3) Rb2–S14 3.246(5) Sb5–S14 2.491(4) Sb10–S15 2.458(4) Rb2–S14 3.362(5) Sb5–S10 2.495(4) Sb10–S12 2.487(4) Rb2–S13 3.501(5) Sb6–S7 2.462(4) Sb10–S2 2.650(4) Rb2–S10 3.750(5) Sb6–S13 2.524(4) Sb10–S5 2.917(4) Rb2–S1 3.883(5) Sb6–S3 2.744(4) 3
Bond Length/Å Bond Length/Å Bond Length/Å
Cs1–S5 3.5874(8) Cs1–S4 4.0854(10) Sb3–S8 2.4957(8) Cs1–S1 3.6343(9) Sb1–S1 2.4308(9) Sb4–S6 2.4270(9) Cs1–S4 3.6897(9) Sb1–S4 2.4821(8) Sb4–S2 2.4685(8) Cs1–S6 3.6994(8) Sb1–S6 2.5693(9) Sb4–S3 2.6977(9) Cs1–S8 3.7147(9) Sb2–S3 2.4510(9) Sb4–S1 2.7688(8) Cs1–S3 3.7307(9) Sb2–S4 2.4767(9) Sb5–S7 2.4162(9) Cs1–S8 3.7499(10) Sb2–S5 2.5616(8) Sb5–S8 2.4843(9) Cs1–S7 3.8033(11) Sb3–S5 2.4717(8) Sb5–S7 2.5690(8)
Table S3. The temperature dependent lattice parameters of 1 and 2. 1 2 Temperature/K a b c Temperature/K a b c 100 8.11537 19.3996 9.04874 100 8.1589 19.539 9.1274 115 8.11685 19.4136 9.05106 115 8.1586 19.5453 9.1267 130 8.11797 19.4211 9.05273 130 8.1637 19.5546 9.1318 145 8.11981 19.4309 9.05446 145 8.1659 19.5592 9.1329 160 8.12063 19.4386 9.05558 160 8.1677 19.5725 9.1342 175 8.12251 19.4458 9.05738 175 8.175 19.5923 9.143 190 8.12436 19.4594 9.06011 190 8.1778 19.6 9.145 205 8.12664 19.4634 9.06171 205 8.1779 19.601 9.1412 220 8.12898 19.4737 9.06343 220 8.1814 19.61 9.1465 235 8.13038 19.4845 9.0646 235 8.1833 19.6173 9.1468 250 8.13308 19.4958 9.06718 250 8.1849 19.6271 9.1489 265 8.1371 19.5083 9.07093 265 8.1904 19.6543 9.1515 280 8.1409 19.5184 9.074 280 8.193 19.662 9.1559 300 8.1485 19.5388 9.0814 300 8.1952 19.6769 9.1572
