Supporting Information. a Department of Chemistry, University of California, Riverside, California 92521,

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1 Supporting Information Assembly of Supertetrahedral T 5 Copper-Indium Sulfide Clusters into Super-Supertetrahedron of Infinite Order Le Wang a, Tao Wu a, Fan Zuo a,, Xiang Zhao a, Xianhui Bu b, Jianzhong Wu c, and Pingyun Feng a a Department of Chemistry, University of California, Riverside, California 92521, b Department of Chemistry and Biochemistry, California State University, Long Beach, California c Department of Chemical and Environmental Engineering, University of California, Riverside, California S1

2 Synthesis procedures and methods Indium (Aldrich), CuI (Aldrich), Sulfur powder (Aldrich), Dibutylamine (DBA) (Acros), Isopropylcyclohexylamine (ipcha) (Aldrich), Ethylene glycol (EG), 3,5-Lutidine (Alfa-Aesar), all chemicals were used as purchased without any further purification. The CIS-11 reported in this study could be synthesized by using different template molecules. By reacting a mixture of In powder (180mg), CuI (30 mg), S (170 mg), in a solution of 4.0g dibutylamine, 2.0g of ethylene glycol and 3.0g water under 150 o C for 5 days, large octahedral lemon yellow crystal beautifully yielded together with brown powders and black aggregates. The powdered impurity compounds yielded could be drifted away by washing using water and ethanol, the crystalline sample collected after such purification varied for each batch from 80mg to 100 mg. And the quality of single crystal could be improved by adding 1.0g of 3, 5-Lutidine as co-solvent. Single crystal for XRD structure analysis was picked from this batch. This material could also be reproducibly synthesized by reacting water (2.0g) and ethylene glycol (2.0g) solution mixture of Indium (120mg), CuI (30mg), sulfur powder (90mg), and isopropylcyclohexylamine (0.6g) under 190 o C for 7 days. The product was yielded as orange yellow tetrahedral crystals and other block polyhedrons with less amount of amorphous powder. The crystal using DBA as template has better morphology and better crystallinity, and the crystal using ipcha as template has better yield. Data of the powder XRD pattern, TGA information, solid state UV-Vis reflectance spectra, and photocatalytic activity tests are all from the sample using DBA as template with co-solvent of 3, 5-Lutidine. Figure S1 View of the CIS-11 structure as face centered cubic close packing of T 5 clusters. S2

3 Figure S2 View of the CIS-11 structure from different crystallographic directions (shown in the diagram) S3

4 Intensity Figure S3 An optical image of crystals synthesized. 300 As Synthesized Simulated Theta Figure S4 Measured and simulated powder XRD patterns for CIS-11. S4

5 Weight % Kubelka-Munt Function CIS ev Photon Energy (ev) Figure S5 The solid state UV-Vis absorption spectrum. CIS Temperature K Figure S6. TGA plot of CIS-11 heated under nitrogen atmosphere. TGA experiment was performed on STDQ-600 with initial temperature of 300K increased to 1200K with 10K per minute under nitrogen environment with a flow rate of 100 micro liters per minute. S5

6 Amount of Hydrogen Generated (umol) Time of Radiation (Hour) Figure S7. Photocatalytic activity for hydrogen generation of CIS-11. The photocatalytic hydrogen evolution reaction with sacrificial reagent of Na 2 S was performed in a quartz round bottom flask, and the incident light from 300w Xe lamp was filtered by both optical filter with cutoff >400nm and an IR filter. In a typical reaction, 200mg of CIS-11 crystals are suspended into 270ml of 0.5 M Na 2 S aqueous solution under vigorous stir. The hydrogen could be generated steadily with a rate of 3.8 μmol h -1 g -1 without any co-catalysts. The catalysts remained active for at least 72 hours with a turnover numbers of 3.7; however, the evolution rate slowed after 40 hour, which may indicate the decomposition of the material under long radiation. Figure S8 Imaginary structures of super-super tetrahedra of T 2, T 3, T 4,. Because of the limitation of the page size, only T 2,4, T 3,4, and T 4,4, which are fragment of T 2, T 3, T 4, are shown here. S6