Benzoate substituents effects on the structure of Zn(II) complexes and 1D 4,4′-bipyridine derived coordination polymers

Francisco Sanchez Ferez, Roger Pou, Laura Bayés-Garciá, Mercè Font-Bardia, Josefina Pons Picart*, Jose Antonio Ayllon Esteve*

*Corresponding author for this work

Research output: Contribution to journalArticleResearchpeer-review

3 Citations (Scopus)

Abstract

The aim of this work is to study the influence of different substituents in two closely related ligands, 3,5-dihydroxybenzoate (3,5-(HO) 2Bz) and 3,5-dimethoxybenzoate (3,5-(MeO) 2Bz), in the structure of zinc complexes. The compound [Zn(3,5-(MeO) 2Bz) 2(CH 3OH)] 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(µ-3,5-(HO) 2Bz)(µ-OH 2)(H 2O) 2]·3,5-(HO) 2Bz·4H 2O} 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) 2Bz) 2(µ-4,4′-bpy)]·2DMSO} n (3) was achieved in dimethylsulfoxide (DMSO) while {[Zn(3,5-(HO) 2Bz) 2(µ-4,4′-bpy)]·4,4′-bpy·1/2CH 3OH} n (4) was formed in methanol (MeOH) as solvent. The reaction of 2 with 4,4′-bpy yielded [Zn 2(μ-3,5-(MeO) 2Bz) 4(µ-4,4′-bpy)] n (5) in methanol, while after recrystallization in boiling water, complex {[Zn(3,5-(MeO) 2Bz) 2(µ-4,4′-bpy)]·H 2O} 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) 2Bz (5 and 6), showed solid state luminescence.

Original languageEnglish
JournalInorganica Chimica Acta
Volume500
DOIs
Publication statusPublished - 24 Jan 2020

Keywords

  • Coordination polymer
  • N-Heterocyclic ligands
  • Photoluminescence properties
  • Supramolecular network
  • Zn(II) complexes

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