Discrete systems and two-dimensional coordination polymers containing potentially multidentate and bridging inorganic anions: Observation of a new type of two-dimensional topology

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• 作者：Arpita Biswas^a ; Arpita Jana^a ; Sohini Sarkar^a ; Hazel A. Sparkes^b ; ^c ; Judith A.K. Howard^b ; Nú ; ria Aliaga-Alcalde^d ; ^{nuria.aliaga@icrea.cat" class="auth_mail} ; Sasankasekhar Mohanta^a ; ^{sm_cu_chem@yahoo.co.in" class="auth_mail}
• 关键词：Coordination polymer ; Bridging ligand ; Cyanometalates ; Magnetic properties ; Diamine ; Two-dimensional
• 刊名：Polyhedron
• 出版年：28 May, 2014
• 年：2014
• 卷：74
• 期：Complete
• 页码：57-66
• 全文大小：2478 K

文摘

The work in this report deals with seven compounds of composition {[Cu^II(dmpn)₂]₃[Fe^III(CN)₆]₂路6H₂O}_n (1), {[Cu^II(dmpn)₂]₃[Co^III(CN)₆]₂路6H₂O}_n (2), {[Cu^II(dmpn)₂]₃[Cr^III(CN)₆]₂路4H₂O}_n (3), {[Cu^II(dmpn)][Ni^II(CN)₄]路H₂O}_n (4), [{Cu^II(dmpn)₂Cl}{Cu^II(dmpn)₂(H₂O)}][Ag^I(CN)₂]Cl₂ (5), [(Cu^II(dmpn)₂(dicyanamide)₂] (6) and [(Ni^II(dmpn)₂(dicyanamide)₂] (7), where dmpn = 2,2-dimethyl-1,3-diaminopropane. Syntheses, characterization and crystal structures of 1-7 along with variable-temperature (2-300 K) magnetic properties of 1 and 3 are described. Compounds 1-4 are cyanide-bridged two-dimensional coordination polymers. Twelve metal-membered ring is formed in 1-3, while both four and eight metal-membered rings are formed in 4. On the other hand, dicyanoargentate(I) in 5 is noncoordinated and dicyanamide in 6 and 7 behaves as monodentate terminal ligand. The coordination polymers in 1-4 and the discrete systems in 5-7 are self-assembled by hydrogen bonding interactions to generate overall three-dimensional supramolecular topologies. A novel structural aspect, two-dimensional network containing both four and eight metal-membered rings, has been observed in the copper(II)-tetracyanonickelate(II) compound 4. Magnetic studies reveal ferromagnetic interaction between Cu^II and Cr^III in 3. In addition, spin-orbit coupling of low-spin Fe^III or weak antiferromagnetic interaction along with intermolecular antiferromagnetic interactions which exist between Cu^II and Fe^III are present in 1.