CdS Nanoparticles Fabricated from the Single-Source Precursor [Cd{Et2NC(S)NP(S)(OiPr)2}2]: In Depth Experimental and Theoretical Studies

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• 作者：Maria G. Babashkina ; Damir A. Safin ; Mariusz P. Mitoraj ; Filip Sagan ; Michael Bolte ; Axel Klein
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：June 1, 2016
• 年：2016
• 卷：16
• 期：6
• 页码：3287-3296
• 全文大小：766K
• 年卷期：0
• ISSN：1528-7505

文摘

Reaction of the diethylammonium salt of N-thiophosphorylated thioureate [Et₂NC(S)NP(S)(OiPr)₂]⁻ (L^–) with CdCl₂ in aqueous ethanol leads to the complex [CdL₂]. The compound crystallizes in the triclinic space group P1̅ with Z = 2 and the metal cation is found in a tetrahedral S₂S′₂ coordination environment formed by the C–S and P–S sulfur atoms. The Hirshfeld surface analysis showed that the structure of [CdL₂] is dominated by H···H, S···H, and O···H contacts. According to charge and energy decomposition scheme ETS-NOCV, topological noncovalent index (NCI) and quantum theory of atoms in molecules (QTAIM) calculations, both inter- and intramolecular noncovalent C–H···S and C–H···H–C interactions are the main factors that stabilize [CdL₂]. Calculated NMR data, based on the GIAO approach, are in very good agreement with experimental data. The complex [CdL₂] is an efficient single-source precursor for the formation of TOPO-capped CdS nanoparticles of about 5 nm diameter with wurtzite structure (TOPO = tri-n-octylphosphine oxide). Their growth was monitored over a period of time by means of UV–vis spectroscopy. From ETS-NOCV modeling, the TOPO molecules were found to strongly adhere to the CdS nanoparticles through dative-covalent Cd–O bonds as well as through secondary noncovalent C–H···Cd and C–H···S interactions. The characteristic band edge luminescence was observed in the emission spectra of all samples. The TEM microscopy showed well-dispersed spherical CdS nanoparticles; the composition was supported by EDX.