Accessing copper-tin-sulfide nanostructures from diorganotin(IV) and copper(I) 2-pyrazinyl thiolates

• Published in: Journal of organometallic chemistry Vol. 887; pp. 24 - 31
• Main Authors: Tyagi, Adish, Kole, Goutam Kumar, Shah, Alpa Y., Wadawale, Amey, Srivastava, A.P., Kumar, Mukesh, Kedarnath, G., Jain, Vimal K.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.05.2019
• Subjects: Copper(I)thiolate; CTS nanostructure; Diorganotin(IV)thiolate; Metal sulfide; Molecular precursors; Diorganotin(IV)thiolate; Copper(I)thiolate; Metal sulfide; CTS nanostructure; Molecular precursors
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/j.jorganchem.2019.02.026

Synthesis of air stable di-tert-butyltin(IV) and copper(I) complexes of 2-pyrazinyl thiolate (2-pyzSH), [tBu2Sn(Spyz)2] (1) and [Cu(Spyz)(PPh3)2] (2), as molecular precursors for metal sulfide nanomaterials is described. These complexes were isolated by the reactions of [tBu2SnCl2] and [CuCl(PPh3)3] with sodium 2-pyrazinyl thiolate at room temperature. The molecular structures of these complexes have been established by single crystal X-ray diffraction analyses and hetero nuclear NMR. The thermal analyses of 1 and 2 revealed closely related decomposition temperatures with the formation of the corresponding metal sulfide. Utility of these complexes as molecular precursors for the preparation of binary (SnS and Cu1.8S) and ternary Cu2SnS3 (CTS) metal sulfide nanostructures has been assessed. The phase purity, morphology and composition of nanostructures were investigated by PXRD, Raman, SEM, TEM and EDS analysis. The band gap of nanostructures as deduced from diffuse reflectance spectroscopy (DRS) are 1.4, 1.8 and 2.0 eV for CTS, SnS and Cu1.8S, respectively which are blue shifted relative to their respective bulk counterpart. It has been demonstrated that role of solvent is highly crucial for the phase purity of CTS nanostructures. The Photo-electrochemical studies revealed that CTS nanostructures pose as better photo responsive material as compared to Cu1.8S. [Display omitted] •Air stable precursors, [tBu2Sn(Spyz)2] and [(PPh3)2Cu(Spyz)] for Cu2SnS3 (CTS) have been synthesized and characterized.•Utility of these precursors for the preparation of binary and ternary nanostructures have been evaluated.•Choice of solvent is imperative for obtaining phase pure nanostructures has been demonstrated.•Band gap and PEC studies reveals that CTS is a better solar cell absorber material compared to the SnS and Cu1.8S.