Synthesis, crystal structure and luminescence of [(CH₃)₃S]₂ZrCl₆

Abstract

The current work reports on the synthesis, crystal structure and optoelectronic properties of (Me₃S)₂ZrCl₆, prepared by reacting the solid precursors (Me₃S)Cl and ZrCl₄ in pyrex tubes at 150 °C under vacuum. According to X-ray powder diffraction and Rietveld analysis, (Me₃S)₂ZrCl₆ crystallizes in the cubic space group Pa-3 (No. 205) with a = 12.4664(1) Å. The crystal structure consists of isolated trigonal pyramidal trimethylsulfonium cations and octahedral [ZrCl₆]^2- anions with weak hydrogen bonds among them and no signs of structural disorder. This 0D-material is stable in air and dissolves in water and dimethylformamide. Raman spectroscopy shows characteristic vibrational modes for the organic and inorganic moieties over the frequency range of 5–3200 cm⁻¹. UV-Vis spectroscopy reveals a large band gap of 5.1 eV and a broadband luminescence with emission maximum at 465 nm in the solid state. The luminescent properties of (Me₃S)₂ZrCl₆ are discussed and compared with those of similar inorganic or metal-organic compounds.

Keywords:

• Trimethylsulfonium cation
• Zr(IV) salts
• organic-inorganic compounds
• ‘defect’ Perovskite structure
• luminescence

Supplementary material

Crystallographic data for the structure reported in this article have been deposited in the Cambridge Crystallographic Data Centre, CCDC-2314424. Copies can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (Internet) + 44-1223/336-033; E-mail: [email protected]].

Acknowledgements

The research project was supported by the Hellenic Foundation for Research and Innovation (H.F.R.I.) under the “2nd Call for H.F.R.I. Research Projects to support Post-Doctoral Researchers” (Project Number: 450). The authors would also like to thank Prof. Ioannis Koutselas for the fruitful discussions.

Disclosure statement

No potential conflict of interest was reported by the author(s).

Additional information

Funding

The research project was supported by the Hellenic Foundation for Research and Innovation (H.F.R.I.) under the “2nd Call for H.F.R.I. Research Projects to support Post-Doctoral Researchers” (Project Number: 450).