Supporting Information for Supertetrahedral Cluster Based In-Se Frameworks with Unique Polyselenide Ion as Linker Chaozhuang Xue, Jian Lin, Huajun Yang, Wei Wang, Xiang Wang, Dandan Hu, Tao Wu * College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu 215123, China Corresponding author email: wutao@suda.edu.cn
General Methods: Materials: Indium (In, 99.9%, powder), selenium (Se, 99.9%, powder), piperidine (PR, >99%, liquid), 3,5-Dimethylpiperidine (3,5-DMPR, >97%, liquid), 1-Methylpiperidine (1-MPR, >99%, liquid), dimethyl formamide (DMF, >99%, liquid), amino 1, 4-dioxane (50%, liquid) and deionized water were all used as supplied without further purification. Synthesis of [µ 3 -Se 4 ] 3.27 [In 49.88 Se 95.92 ] (C 5 H 12 N) 26.0 (C 2 H 8 N) 42.4 (1): Compound 1 was obtained by replacing water with DMF in the typical preparation process of CSZ-5-InSe crystals, i.e. solvothermal reaction of selenium powder (250 mg, 3.166 mmol) with indium metal (80 mg, 0.697 mmol) in the mixed solvents of piperidine (PR, 2.5 ml) and dimethyl formamide (DMF, 3.0 ml) at 170 for 5 days. 110 mg of yellow pyramid crystals were obtained. Dimethylamine (C 2 H 8 N) in 1 is derived from the decomposition of DMF. Anal. calc.: C, 13.92%; N, 5.17%; H, 3.54%. Found: C, 13.22%; N, 4.56%; H, 3.27%. Synthesis of [In 4 Se 10 ] (C 7 H 16 N) 1.8 (C 2 H 8 N) 2.2 (2): Compound 2 was synthesized by solvothermal reaction of selenium powder (250 mg, 3.166 mmol) with indium metal (80 mg, 0.697 mmol) in the mixed solvents of 1,4-dioxane (1.0 ml), 3,5-dimethylpiperidine (3,5-DMPR, 2.0 ml), and dimethyl formamide (DMF, 1.0 ml) at 170 for 7 days. The autoclave was subsequently allowed to cool to room temperature. About 60 mg of orange rodlike crystal were obtained. Dimethylamine (C 2 H 8 N) in 2 is derived from the decomposition of
DMF. Anal. calc.: C, 13.12%; N, 3.60%; H, 3.00%. Found: C, 14.13%; N, 3.87%; H, 3.31%. Synthesis of [In 20 Se 39 ] (C 6 H 14 N) 12 (3): Compound 3 was obtained by solvothermal reaction of selenium powder (400 mg, 5.066 mmol) with indium metal (114.818 mg, 1.0 mmol) in the mixed solvents of deionized water (1.0 ml) and 1-methylpiperidine (1-MPR, 5 ml) at 180 for 6 days. 80 mg of orange-yellow irregular crystal can be obtained. Anal. calc.: C, 13.14%; N, 2.55%; H, 2.57%. Found: C, 13.06%; N, 2.97%; H, 2.75%. Structure Characterization. Single-crystal X-ray diffraction measurements were performed on Bruker Photon II CPAD diffractometer with nitrogen-flow temperature controlled using graphite-monchromated Mo-Kα (λ =0.71073 Å) radiation at 120 K. The structure was solved by direct method using SHELXS-97 and the refinement against all reflections of the compound was performed using SHELXL-97. The protonated organic amines located in the void space of the framework cannot be identified owing to their serious disorder and hence the squeeze subprogram has been performed. Relevant crystal data, collection parameters, and refinement results of compound 1 3 were summarized in the Table S1. Powder X-ray diffraction (PXRD) data were collected on a desktop diffractometer (D2 PHASER, Bruker, Germany) using Cu-K α (λ=1.54056 Å) radiation operated at 30 kv and 10 ma.
Elemental Analysis: Energy dispersive spectroscopy (EDS) analysis was performed on scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) detector. An accelerating voltage of 25 kv and 40 s accumulation time were applied. Elemental analysis of C, H and N was performed on VARIDEL III elemental analyzer. Ion-Exchanging Experiments. 10 mg of as-synthesized sample was added into 30 ml of CsCl (1M) solution. The mixture was continuously shaken for 24 h at room temperature. Then the polycrystalline materials were filtrated and washed by water and ethanol for several times, and then collected for EDS and EA measurements. Optical Measurements: Room-temperature solid-state UV-Vis diffusion reflectance spectra of crystal samples were measured on a SHIMADZU UV-3600 UV-Vis-NIR spectrophotometer, by using BaSO 4 powder as the reflectance reference. The absorption spectra were calculated from reflectance spectra by using the Kubelka-Munk function: F(R) =α/s= (1-R) 2 /2R, where R, α, and S are the reflection, the absorption and the scattering coefficient, respectively. In order to determine band edge of the semiconductor, the relation between the absorption coefficients (α) and the incident photon energy (hυ) is exhibited as αhυ= A (hυ E g ) 1/2, where A is a constant that relates to the effective masses associated with the valence and conduction bands, and E g is the optical transition gap of the solid material. The band gap of the obtained samples
can be determined from the Tauc plot with [F(R)*hυ] 2 vs. hυ by extrapolating the linear region to the abscissa. Photoelectrochemical Experiment: 2 mg of the as-synthesized crystals were first grounded into fine powders using a marble and pestle, and then added into 200 µl of 0.5 % nafion (5% in water and isopropanol). After ultrasonic treatment for 10 minutes, the obtained suspensions were dropped onto the surface of ITO substrate, and then dried at room temperature. The photocurrent experiments were performed on a CHI760E electrochemistry workstation in a three-electrode electrochemical cell, with the sample coated ITO glass (the effective area is around 1 cm 2 ) as the working electrode, a Pt wire as the auxiliary electrode, and a saturated calomel electrode (SCE) as the reference electrode. The light source is a 150 W high pressure xenon lamp, located 20 cm away from the surface of the ITO electrode. Sodium sulfate aqueous solution (0.5 M, 100 ml) was used as the supporting electrolyte.
Figure S1. SEM images and EDS results of compounds 1-3. Figure S2. The simulated and experimental PXRD patterns of compound 1.
Figure S3. The simulated and experimental PXRD patterns of compound 2. Figure S4. The simulated and experimental PXRD patterns of compound 3.
Figure S5. TGA curves of compound (1), (2) and (3). The initial gradual weight loss before 220ºC (165ºC for 1) could be attributed to loss of moisture adsorbed on the surface of samples. An abrupt weight loss between 220-350ºC (165-350ºC for 1) is attributed to the carbonization of template. Figure S6. Raman spectra for compound 1, 2 and 3. The wide band in the range of 262-277cm -1 is attributed to Se-Se bonds.
Figure S7. The µ 3 -Se 4 and µ 3 -T1 occupy on the same position in compound 1. Figure S8. Three kinds of windows in compound 1 with large apertures.
Figure S9. Simplified structure of compound 1. (a) T2 cluster and µ 3 -Se 4 are treated as nodes. (b) The simplified cages α and cages β. (c) Interrupted site in cages α (left); normal diamond topology (right). (d) Cage α is surround with six cages β in ab plane and two cages β in c-axis direction in simplified framework. (e) Cage β is surrounded by three cages α and three cages β in ab plane and one cage α and β in the c-axis direction in the simplified framework. (f) The simplified network viewed from c-axis direction.
Figure S10. Cage β is surrounded by three cages α and three cages β in ab plane, and one cage α and one cage β in the c-axis direction in compound 1. Figure S11. (a) The network of compound 2 and the elongated adamantane cage (T2 as building blocks) in the form of polyhedron (above) and simplified one (below). (b-c) Two kinds of windows (Window D and window E) of elongated adamantane cage in compound 2.
Figure S12. (a) The interpenetrated structure of compound 3 composed by distorted adamantane cages in the form of polyhedron (above) and simplified one (below) (T3 as building block). (b-c) Two kinds of windows (Window F and window G) of the elongated adamantane cage in compound 3.
Figure S13. PXRD patterns of compound 1, 2 and 3 after ion exchange for 24 h at room temperature. Figure S14. SEM images and EDS results of Cs-exchanged 1 (a) and 3 (b).
Table S1. Crystal data, parameters and refinement results of compounds. Empirical formula a [In 49.9 Se 95.9 ][Se 4 ] 3.3 (C 5 H 12 N) 26.0 (C 2 H 8 N) 42.4 Compound 1 Compound 2 Compound 3 [In 4 Se 10 ] (C 7 H 16 N) 1.8 (C 2 H 8 N) 2.2 [In 20 Se 39 ] (C 6 H 14 N) 12 Formula weight a 18538.28 1552.89 6577.99 Crystal system Trigonal Orthorhombic Monoclinic Z 6 8 4 Space group R-3/c Pnma P2 1 /c a(å) 24.56 13.07 35.55 b(å) 24356 21.16 19.71 c(å) 67.74 15.08 23.32 α(deg.) 90.00 90.00 90.00 β(deg.) 90.00 90.00 101.46 γ(deg.) 120.00 90.00 90.00 V (Å 3 ) 35378 4171.3 16017.9 F(000) 18309.8 2144.0 9224.0 D c (g cm -3 ) 2.003 1.989 2.229 µ (mm -1 ) 10.730 10.895 11.684 Crystal morphology Bulk Stick Flaky 2θ max (deg.) 28.2 29.63 15.89 Collected reflections 56443 16189 58292 Independent reflections 6943 (R int = 0.0352) 3773 (R int = 0.0432) 7664 Observed reflections 6177 2949 6004 (R int = 0.0588) Parameters/restrain/data 267/0/8799 163/0/5760 428/0/5595 GOF on F 2 1.062 0.631 1.09 R 1, wr 2 (I>2σ(I)) b 0.0811, 0.2373 0.0348, 0.1358 0.0705, 0.2298 R 1, wr 2 (all data) 0.0894, 0.2464 0.0492, 0.1566 0.0882, 0.2434 Note: a according to refinement result. b R 1 = F o - F c / F o, wr 2 = [ w(f o 2 -F c 2 ) 2 / w (F o 2 ) 2 ] 1/2 Table S2. The results of elemental analysis of pristine compound 1, compound 3
and the corresponding Cs + -exchanged samples. Elements (wt.) N (%) C (%) H (%) Pristine compound 1 4.56 13.22 3.27 Cs + -exchanged 1 0.00 0.63 1.08 Pristine compound 3 2.97 13.06 2.75 Cs + -exchanged 3 0.25 1.17 1.01