Ligand-Directed Assembly of a Series of Complexes Bearing Thiourea-Based Carboxylates

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• 作者：Huijie Lu ; Yanyan Zhu ; Nan Chen ; Yongchao Gao ; Xiaofang Guo ; Gang Li ; Mingsheng Tang
• 刊名：Crystal Growth & Design
• 出版年：2011
• 出版时间：December 7, 2011
• 年：2011
• 卷：11
• 期：12
• 页码：5241-5252
• 全文大小：1363K
• 年卷期：v.11,no.12(December 7, 2011)
• ISSN：1528-7505

文摘

Three interesting copper complexes, {[Cu^I₆Cu^II₆L¹₆(H₂O)₃(CH₃OH)₆]路5H₂O路3CH₃OH}_n (2), [Cu^I₆Cu^II₆L²₆(H₂O)₁₀]_n (3), and [Cu₃L³₂(CH₃OH)₄] (4) [H₃L¹ = 2-(3-benzoylthioureido)ethanoic acid, H₃L² = 2-(3-benzoylthioureido)propionic acid, H₃L³ = 2-(3-benzoylthioureido)benzoic acid], have been synthesized and characterized by single-crystal X-ray diffraction, XPS, elemental analyses, EPR, and IR spectra. Polymer 2 was synthesized by the reaction of single crystals of {[Ln₂(H₂L¹)₄(Phen)₂(NO₃)₂]路CH₃OH} [Ln = Pr (1a), Nd (1b), or Ho (1c), Phen = 1,10-phenanthroline] with Cu(OAc)₂ in aqueous DMF. Compounds 3 and 4 were prepared by Cu(OAc)₂ directly reacting with H₃L² or H₃L³ in solution, respectively. Complexes 2 and 3 are rare 2D cluster polymers containing unique mixed-valence [Cu^I₆Cu^II₆L¹₆] or [Cu^I₆Cu^II₆L²₆] subunits. Compound 4 is a trinuclear copper(II) complex, in which two triply deprotonated (L³)^{3鈥?/sup> ligands bridge three Cu2+ ions. The theoretical predication of the substituent effect of the three triply deprotonated ligands (L1)3鈥?/sup>, (L2)3鈥?/sup>, and (L3)3鈥?/sup> has been presented. The thermal properties of complexes 2鈥?b>4 have been determined as well. Also, it is discovered that there exists weak antiferromagnetic coupling between the neighboring Cu(II) ions in 2, 3, or 4, respectively; the best fittings to the experimental magnetic susceptibilities gave J = 鈭?.63 cm鈥? and g = 2.14 for 3 and J = 鈭?2.06 cm鈥?, J鈥?/i> = 鈭?.01 cm鈥?, and g = 2.21 for 4.}