Crystal system: triclinic
| a: | 12.0929 (±0.0005) Å |
| b: | 12.1407 (±0.0006) Å |
| c: | 32.496 (±0.0015) Å |
| α: | 84.6775 (±0.0016)° |
| β: | 82.833 (±0.0015)° |
| γ: | 89.9763 (±0.0015)° |
Starting materials: tert-Butyl(2-(5-bromothiophen-2-yl)ethyl)carbamate, Pd2(dba)3, P(o-tol)¬3, tributyl(3,3”-dimethyl-[2,2’:5’,2”-terthiophen]-5-yl)stannane
Product: thin, dark red/black plate-like crystals
Description: The organic salt 4Tm-Boc was synthesized first by mixing tert-Butyl(2-(5-bromothiophen-2-yl)ethyl)carbamate (612 mg, 2 mmol), Pd2(dba)3 (37 mg, 2 mol%), P(o-tol)¬3 (49 mg, 8 mol%) and tributyl(3,3”-dimethyl-[2,2’:5’,2”-terthiophen]-5-yl)stannane (2.2 mmol) in a 100 mL Schlenk tube. The air was then replaced with argon, and toluene (20 mL) was added to the mixture. The mixture was stirred for 0.5 hours at 100º C, cooled to room temperature, water was added, and the solution was extracted via dichloromethane (DCM). The organic layers were combined, washed, and dried. Next, 4Tm-Boc (1 mmol) was dissolved in 20 mL methanol, aqueous HI solution was added, and the solution was stirred for 6 hours. Solid 4TmI salt resulted. Single crystals of (4Tm)2SnI4 were obtained by dissolving stoichiometric amounts of 4TmI and SnI2 in gamma-bytrolactone (GBL) (0.1 M), and then performing vapor diffusion of chloroform and chlorobenzene. This yielded thin dark red/black plates.
Method: Single-crystal X-Ray Diffraction
Description: A Bruker Quest diffractometer with kappa geometry, I-μ-S microsource X-ray tube (Cu Kα radiation, λ = 1.54178 Å), Photon2 CMOS area detector, and multilayer mirror for monochromatization was used. Data was scanned and corrected with APEX3, space groups were solved using XPREP in SHELXTL
Crystal system: triclinic
| Band gap (fundamental), eV |
|---|
Code: VASP version 5.4.4
Level of theory: DFT
K-point grid: 4x4x2
Basis set definition: PAW
Comment: K-path of triclinic unit cell was used to calculate band structure. Band gaps were derived from band structure
Starting materials: tert-Butyl(2-(5-bromothiophen-2-yl)ethyl)carbamate, Pd2(dba)3, P(o-tol)¬3, tributyl(3,3”-dimethyl-[2,2’:5’,2”-terthiophen]-5-yl)stannane
Product: film
Description: The organic salt 4Tm-Boc was synthesized first by mixing tert-Butyl(2-(5-bromothiophen-2-yl)ethyl)carbamate (612 mg, 2 mmol), Pd2(dba)3 (37 mg, 2 mol%), P(o-tol)¬3 (49 mg, 8 mol%) and tributyl(3,3”-dimethyl-[2,2’:5’,2”-terthiophen]-5-yl)stannane (2.2 mmol) in a 100 mL Schlenk tube. The air was then replaced with argon, and toluene (20 mL) was added to the mixture. The mixture was stirred for 0.5 hours at 100º C, cooled to room temperature, water was added, and the solution was extracted via dichloromethane (DCM). The organic layers were combined, washed, and dried. Next, 4Tm-Boc (1 mmol) was dissolved in 20 mL methanol, aqueous HI solution was added, and the solution was stirred for 6 hours. Solid 4TmI salt resulted. Single crystals of (4Tm)2SnI4 were obtained by dissolving stoichiometric amounts of 4TmI and SnI2 in gamma-bytrolactone (GBL) (0.1 M), and then performing vapor diffusion of chloroform and chlorobenzene. This yielded thin dark red/black plates. 4TmI (53.0 mg, 100 μmol) and SnI2 (23.0 mg, 50 μmol) were dissolved in 1 mL of anhydrous DMF/DMSO (10/1) at 70 degrees C. The (4Tm)2SnI4 solution was allowed to cool to room temperature and was spin coated at 4000 rpm for 60 s on clean Si/SiO2 wafers or quartz slides. The films were annealed at 180 degrees C on a hot plate for 10 min in nitrogen.
Method: Photoluminescence
Comment: Details are not available in the paper
Starting materials: tert-Butyl(2-(5-bromothiophen-2-yl)ethyl)carbamate, Pd2(dba)3, P(o-tol)¬3, tributyl(3,3”-dimethyl-[2,2’:5’,2”-terthiophen]-5-yl)stannane
Product: film
Description: The organic salt 4Tm-Boc was synthesized first by mixing tert-Butyl(2-(5-bromothiophen-2-yl)ethyl)carbamate (612 mg, 2 mmol), Pd2(dba)3 (37 mg, 2 mol%), P(o-tol)¬3 (49 mg, 8 mol%) and tributyl(3,3”-dimethyl-[2,2’:5’,2”-terthiophen]-5-yl)stannane (2.2 mmol) in a 100 mL Schlenk tube. The air was then replaced with argon, and toluene (20 mL) was added to the mixture. The mixture was stirred for 0.5 hours at 100º C, cooled to room temperature, water was added, and the solution was extracted via dichloromethane (DCM). The organic layers were combined, washed, and dried. Next, 4Tm-Boc (1 mmol) was dissolved in 20 mL methanol, aqueous HI solution was added, and the solution was stirred for 6 hours. Solid 4TmI salt resulted. Single crystals of (4Tm)2SnI4 were obtained by dissolving stoichiometric amounts of 4TmI and SnI2 in gamma-bytrolactone (GBL) (0.1 M), and then performing vapor diffusion of chloroform and chlorobenzene. This yielded thin dark red/black plates. 4TmI (53.0 mg, 100 μmol) and SnI2 (23.0 mg, 50 μmol) were dissolved in 1 mL of anhydrous DMF/DMSO (10/1) at 70 degrees C. The (4Tm)2SnI4 solution was allowed to cool to room temperature and was spin coated at 4000 rpm for 60 s on clean Si/SiO2 wafers or quartz slides. The films were annealed at 180 degrees C on a hot plate for 10 min in nitrogen.
Method: UV-vis absorption
Description: Obtained using an Agilent UV-Vis-NIR Cary-5000 spectrometer in transmission mode.