Synthesis, crystal structure, supramolecular associations and third-order non-linear optical (NLO) properties of some organotellurium (IV) derivatives

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• 作者：Prakash C. Srivastava ; Vikas Singh ; Shrinkhala Dwivedi ; Tripurari Pujan ; Arun K. Bhuj ; Ray J. Butcher ; M. Bala Murali Krishna ; D. Narayana Rao
• 关键词：Organotellurium (IV) dicarboxylates ; Organotellurium (IV) dithiocarbamates ; Supramolecular assemblies ; Third order non-linear optical properties
• 刊名：Polyhedron
• 出版年：2012
• 出版时间：25 July, 2012
• 年：2012
• 卷：42
• 期：1
• 页码：36-42
• 全文大小：923 K

文摘

Reactions of acyclic and cyclic organotellurium (IV) compounds [R₂TeI₂ {R₂ = (C₂H₅)₂, (n-C₃H₇)₂, C₅H₁₀}] with the silver salt of carboxylic acids and sodium diethyldithiocarbamate form the organotellurium (IV) complexes (C₂H₅)₂Te(4-NO₂C₆H₄OCO)₂ (class=""boldFont"">1), (C₂H₅)₂Te(C₆H₅CHCHOCO)₂ (class=""boldFont"">2), (n-C₃H₇)₂Te(C₆H₅OCO)₂ (class=""boldFont"">3), (n-C₃H₇)₂Te(4-NO₂C₆H₄OCO)₂ (class=""boldFont"">4), (n-C₃H₇)₂Te(3,5-NO₂C₆H₃OCO)₂ (class=""boldFont"">5), (n-C₃H₇)₂Te(4-OCH₃C₆H₄OCO)₂ (class=""boldFont"">6), (n-C₃H₇)₂Te(C₆H₅CHCHOCO)₂ (class=""boldFont"">7), C₅H₁₀Te(C₆H₅CHCHOCO)₂ (class=""boldFont"">8) and C₅H₁₀TeCl[SCSN-(C₂H₅)₂] (class=""boldFont"">9). The X-ray structures of some of these organotellurium (IV) derivatives indicate that they possess ¦×TBP geometry and dimeric and tetrameric supramolecular associations are achieved through cooperative participation of inter- and/or intramolecular Te¡¤¡¤¡¤O secondary bonds and/or C-H¡¤¡¤¡¤O hydrogen bonds. The intramolecular Te¡¤¡¤¡¤O secondary bond lengths seem to be dependent on the cis- and trans-position placements of free oxygens of the carboxylate groups. It is found that the third-order non-linear optical susceptibilities (¦Ö⁽³⁾) of these complexes are in the range 7.21-8.20 ¡Á 10^?14 esu and the second order hyperpolarizabilities (¦Ã) are in the range 4.89-5.56 ¡Á 10^?32 esu. The presence of the telluracyclopentane (C₅H₁₀Te) cyclic organic group and cinnamate (C₆H₅CHCHOCO)/diethyldithiocarbamate (SCSN(C₂H₅)₂) ligands having conjugation in the organotellurium (IV) derivatives (class=""boldFont"">8 and class=""boldFont"">9), appears to be responsible for the higher ¦Ö⁽³⁾ and ¦Ã values.