Journal
INORGANICA CHIMICA ACTA
Volume 500, Issue -, Pages -Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2019.119218
Keywords
Zn(II) complexes; N-Heterocyclic ligands; Coordination polymer; Supramolecular network; Photoluminescence properties
Categories
Funding
- Spanish National Plan of Research [CB615921, MAT2015-65756R, CTQ2017-83632-CO2-P1]
- Generalitat de Catalunya [2017SGR1687]
- Fundacio La Caixa [CB616406]
- Universitat Autonoma de Barcelona
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The aim of this work is to study the influence of different substituents in two closely related ligands, 3,5-dihydroxybenzoate (3,5-(HO)(2)Bz) and 3,5-dimethoxybenzoate (3,5-(MeO)(2)Bz), in the structure of zinc complexes. The compound [Zn(3,5-(MeO)(2)Bz)(2)(CH3OH)](2) (2) has been synthesized, characterized and its crystal structure elucidated, showing a paddle wheel type dinuclear molecule, with four bridging carboxylate ligands in a syn-syn coordination mode and methanol molecules in the apical positions. This discrete structural array is different than the polymeric structure observed in {[Zn(mu-3,5-(HO)(2)Bz)(mu-OH2)(H2O)(2)]center dot 3,5-(HO)(2)Bz center dot 4H(2)O}(n), previously reported in our group. These two zinc complexes were used as precursor for the synthesis of coordination polymers (CPs) with the 4,4'-bipyridine (4,4'-bpy) linker. The solvent used in their synthesis influences the chemical composition of this CPs. Thus, {[Zn(3,5-(HO)(2)Bz)(2)(mu-4,4'-bpy)]center dot 2DMSO}(n) (3) was achieved in dimethylsulfoxide (DMSO) while {[Zn(3,5-(HO)(2)Bz)(2)(mu-4,4'-bpy)]center dot 4,4'-bpy center dot 1/2CH(3)OH}(n) (4) was formed in methanol (MeOH) as solvent. The reaction of 2 with 4,4'-bpy yielded [Zn-2(mu-3,5-(MeO)(2)Bz)4(mu-4,4'-bpy)](n) (5) in methanol, while after recrystallization in boiling water, complex {[Zn(3,5-(MeO)(2)Bz)(2)(mu-4,4'-bpy)]center dot H2O}(n) (6) was isolated in low yield. This compound 6 can also be synthesized by a mechanochemical approach, using water in a liquid assisted grinding. The crystal structures of complexes 3, 4 and 6 were elucidated, all three showing zigzag polymeric arrays. Both polymers containing 3,5-(MeO)(2)Bz (5 and 6), showed solid state luminescence.
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