Anagostic, mono- and hexahapta interactions in Tl(I) dithiocarbamates: A new precursor for the preparation of Tl₂S nanoparticles

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• 作者：Govindaraju Gomathi^a ; Subbiah Thirumaran^a ; ^{sthirumaran@yahoo.com" class="auth_mail" title="E-mail the corresponding author} ; Samuele Ciattini^b
• 关键词：Thallium(I) dithiocarbamates ; X-ray structure ; Anagostic interaction ; Tl2S nanoparticles ; Powder X-ray diffraction
• 刊名：Polyhedron
• 出版年：2015
• 出版时间：14 December 2015
• 年：2015
• 卷：102
• 期：Complete
• 页码：424-433
• 全文大小：2799 K

文摘

Two new homoleptic complexes, [Tl(bzfdtc)]₂ (1) and [Tl(bu_2-OHbzdtc)]₂ (2) (where bzfdtc = N-benzyl-N-furfuryldithiocarbamate and bu_2-OHbzdtc = (N-butyl-N-(2-hydroxybenzyl)dithiocarbamate), have been prepared and characterized by IR, NMR (¹H and ¹³C), UV–Vis spectroscopy, cyclic voltammetry and single crystal X-ray structural analysis. X-ray crystallography revealed that both complexes are dimers. Both complexes show two monohapta Tl⋯C(S₂) interactions. The Tl⋯Tl distances are 3.635 and 3.719 Å for 1 and 2, respectively. The phenyl ring of the bzfdtc ligand is coordinated (by a η⁶ interaction) to the Tl⁺ ion in complex 1. A rare intramolecular anagostic C–H⋯Tl interaction is observed in complex 2. Thallium sulfide nanoparticle samples 3 and 4 have been prepared from complex 1 using conventional heating and microwave irradiation, respectively. Samples 3 and 4 have been characterized by PXRD, EDAX, HR-TEM, UV–Vis absorption and fluorescence spectroscopy. PXRD measurements revealed rhombohedral and hexagonal phases for samples 3 and 4, respectively. EDAX confirmed the formation of Tl₂S. HR-TEM images showed that the size and morphology of the Tl₂S nanoparticles are affected by the method of preparation (conventional heating compared to microwave irradiation).