Homoleptic platinum(II) and palladium(II) organothiolates and phenylselenolates: solvothermal synthesis, structural determination, optical properties, and single-source precursors for PdSe and PdS nanocrystals

Chui, S. S.-Y., Low, K.-H., Lu, J., Roy, V.A.L. , Chan, S. L.-F. and Che, C.-M. (2010) Homoleptic platinum(II) and palladium(II) organothiolates and phenylselenolates: solvothermal synthesis, structural determination, optical properties, and single-source precursors for PdSe and PdS nanocrystals. Chemistry: An Asian Journal, 5(9), pp. 2062-2074. (doi: 10.1002/asia.201000233) (PMID:20665775)

Abstract

Homoleptic d8‐metal organothiolates and phenylselenolates [M(EC6H5)2]∞ (E=S, M=Pt 1, M=Pd 2, M=Ni 5; E=Se, M=Pt 3, M=Pd 4) were prepared as crystalline solids under solvothermal conditions. Their structures were solved using powder X‐ray diffraction data. In each case, the EC6H5 (E=S, Se) ligand binds to two metal ions (M=Pt, Pd, and Ni) to form chain‐like structures with planar (in 1) or zig‐zag (in 2, 3, 4, 5) conformations. The [M(SR)2]∞ complexes (M=Pt, R=4‐tert‐butylphenyl 6; R=2‐naphthyl 8; R=4‐nitrophenyl 10 and M=Pd, R=4‐tert‐butylphenyl 7; R=2‐naphthyl 9; R=4‐nitrophenyl 11) were prepared under similar solvothermal conditions. Based on the XPS binding energies and elemental analyses, complexes 6, 7, 8, 9, 10, 11 have the same [M(SR)2]∞ formulation as 1 and 2. The cyclic complex [Pd6(SCH3)12] 12 was prepared as a crystalline solid by solvothermal annealing treatment of the amorphous precipitate. A chain‐like polymer structure is proposed for both [Pd(SC12H25)2]∞ 13 and [Pd(SC16H33)2]∞ 14; these polymeric chains self‐assemble to give layer‐like structures. Solid‐state diffuse reflectance spectra reveal that the optical band gap Eg (eV) of complexes 1, 6, 8, 10 and of 2, 7, 9, 11 are in the range of 2.10–3.00 eV and 2.10–2.63 eV, respectively, and 5 has the lowest Eg value (1.72 eV). Heating solid samples of 4 and 13 under solvothermal conditions afforded phase‐pure Pd17Se15 and PdS nanocrystals, respectively. Field‐effect transistors fabricated with a drop‐cast thin film made from Pd17Se15 nanocrystals prior treated with an ethanolic solution of 1‐hexadecanethiol displayed ambipolar charge transporting properties with hole and electron mobility being 7×10−2 cm2 V−1 s−1 and 6×10−2 cm2 V−1 s−1, respectively.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Vellaisamy, Professor Roy
• Authors: Chui, S. S.-Y., Low, K.-H., Lu, J., Roy, V.A.L., Chan, S. L.-F., and Che, C.-M.
• College/School: College of Science and Engineering > School of Engineering
• Journal Name: Chemistry: An Asian Journal
• Publisher: Wiley
• ISSN: 1861-4728
• ISSN (Online): 1861-471X
• Published Online: 27 July 2010