NDLI: Structures and magnetic properties of copper(II) and manganese(II) polymers derived from pseudohalides and a flexible zwitterionic dicarboxylate ligand

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Yi, Xiu-chun Wang, Xuan Gao, En-qing Wang, Kun Li, Xiu-bing
Description	Author Affiliation: Wang K ( Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062, P. R. China.)
Abstract	The flexible zwitterionic dicarboxylate ligand 1,4-bis(4-carboxylato-1-pyridinium)butane (bcpb) assumes different conformations to collaborate with pseudohalides in various coordination modes to produce coordination polymers in which distinct anionic motifs with mixed carboxylate and pseudohalide bridges are interlinked by the cationic butylenebis(pyridinium) tethers. The Cu(II) compound, $[Cu_{2}(bcpb)(N_{3})_{4}]n·nH_{2}O$ (1), is a 1D coordination polymer based on the defective dicubane-like $[Cu_{4}(μ_{3}-1,1,1-N_{3})_{2}(μ-1,1-N_{3})_{2}(μ-1,1-OCO)_{2}]$ cluster. With Mn(II), four distinct 3D coordination polymers , $[Mn_{4}(bcpb)_{4}(N_{3})(H_{2}O)_{4}]_{n}(ClO_{4})_{7n}·nCH_{3}OH·3nH_{2}O$ (2), $[Mn_{2.5}(bcpb)(N_{3})_{5}(H_{2}O)_{2}]_{n}$ (3), $[Mn_{2}(bcpb)(N_{3})_{4}]_{n}·nH_{2}O$ (4), and $[Mn_{2}(bcpb)(NCO)_{4}]_{n}·nH_{2}O$ (5), were characterized. 2 is the first Mn(II) compound with the rare $μ_{4}-1,1,3,3$ azide bridge and exhibits an unusual 3D framework based on the $[Mn_{4}(μ_{4}-1,1,3,3-N_{3})(μ-1,3-OCO)_{6}]$ cluster. In 3, the unique undulated honeycomb-like $[Mn_{2}(μ-1,3-N_{3})_{3}]_{n}$ layers are interlinked into a 3D framework by disordered $[Mn(μ-1,1-N_{3})_{4}(μ-1,3-OCO)_{2}]$ and $[(O_{aqua}–H)_{2}⋯OCO]_{2}$ moieties, and the bcpb ligands serve as additional interlayer linkers to lead to the rare self-catenated $6^{6}$ net. 4 and 5 show 3-fold interpenetrated 3D frameworks based on the chains with $(μ-1,1-N_{3})_{2}(μ-1,3-OCO)$ and $(μ-N,N-NCO)_{2}(μ-1,3-OCO)$ bridges, respectively. Magnetic studies indicated that 1 shows competing ferromagnetic and antiferromagnetic interactions. Compounds 2–5 all show antiferromagnetic coupling between Mn(II) ions, while 3 shows 3D ordering. Analyses of magneto-structural data suggest a general trend that the antiferromagnetic interaction through $(μ-1,1-N_{3})_{2}(μ-1,3-OCO)$ or $(μ-N,N-NCO)_{2}(μ-1,3-OCO)$ increases with a decrease of the Mn⋯Mn distance.
ISSN	14779226
Issue Number	24
Journal	Dalton Trans.
Volume Number	42
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2013-06-28
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Chemistry
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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