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Joining of trinuclear (CuL)2M (M = MnII and CdII) nodes by 1,3- and 1,4-benzenedicarboxylate linkers: Positional isomeric effect on co-crystallization

Abstract

Four new one-dimensional coordination polymers {[(CuL)2Cd(p-BDC)]•H2O}n (1), {[(CuL)2Mn(p-BDC)]•H2O}n (2), {[(CuL)2Cd(m-BDC)][(CuL)2]}n (3), {[(CuL)2Mn(m-BDC)][(CuL)2]}n (4), (where H2L = N,N'-bis(-methylsalicylidene)-1,3-propanediamine), have been synthesized using bimetallic trinuclear nodes, [(CuL)2M] (where MII is MnII/CdII and p-BDC and m-BDC are 1,4- and 1,3-benzenedicarboxylate, respectively). Crystal structures show that all four complexes form 1D chain in which the heterometallic linear trinuclear nodes are connected by syn-syn bridging dicarboxylate linkers. However, in 1 and 2 the nodes which are connected by linear p-BDC are parallel to each other whereas in 3 and 4 the nodes are inclined towards each other to be connected by angular m-BDC linker. Moreover, complexes 3 and 4 are co-crystallized with dimeric CuII unit which are accommodated in the cavities between polymeric chains. This difference in solid state crystal packing is explained theoretically by DFT calculations of complexes 1 and 3 considering the positional isomeric effect of dicarboxylate linkers. Variable temperature magnetic susceptibility measurements of complexes 2 and 4 indicate antiferromagnetic interactions between the CuII and MnII centers with J = –13.08 and –12.11cm-1 for 2 and 4, respectively.

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Publication details

The article was received on 16 Jul 2018, accepted on 08 Sep 2018 and first published on 10 Sep 2018


Article type: Paper
DOI: 10.1039/C8CE01168K
Citation: CrystEngComm, 2018, Accepted Manuscript
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    Joining of trinuclear (CuL)2M (M = MnII and CdII) nodes by 1,3- and 1,4-benzenedicarboxylate linkers: Positional isomeric effect on co-crystallization

    S. Dutta, S. Jana, P. Mahapatra, A. Bauza, A. Frontera and A. Ghosh, CrystEngComm, 2018, Accepted Manuscript , DOI: 10.1039/C8CE01168K

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