Tuning the microstructures of decavanadate-based supramolecular hybrids via regularly changing the spacers of bis(triazole) ligands

Abstract

With tuning the ligands from bte, btp, btb to bth, four new decavanadate-based metal-organic hybrid compounds, [Zn(bte)(H 2 O) 4 ][Zn 2 (bte)(H 2 O) 10 ](V 10 O 28 )•8H 2 O, [Zn 2 (btp) 4 (H 2 O) 6 ](H 2 V 10 O 28 )•4H 2 O, [Zn(H 2 O) 6 ][Zn 2 (btb) 2 V 10 O 28 (H 2 O) 6 ]•4H 2 O, and [Zn 2 (bth)(H 2 O) 10 ](H 2 V 10 O 28 )•6H 2 O (bte = 1,2-bis(1,2,4have been synthesized under conventional conditions. The four compounds represent the first examples of decavanadate-based metal-organic hybrids constructed by Zn-bis(triazole) complexes. Their structural analyses show that the four compounds possess different Zn-bis(triazole) structural motifs and various finally structures, which verifies that regular changing the spacers of ligands is an effective strategy to tuning the structures of polyoxometalate-based hybrids. Also, the electrochemical studies show that the compounds have good electrocatalytic activities towards oxidation of nitrite molecules ascribed to V-centers.

A Robust Open Framework Formed by Decavanadate Clusters and Copper(II) Complexes of Macrocyclic Polyamines: Permanent Microporosity and Catalytic Oxidation of Cycloalkanes

“…While the coordinative role of small polyoxovanadate clusters (e.g., [V 4 O 12 ] 4– ) toward transition-metal complexes has been long documented, most of the decavanadate–metalorganic hybrids known at present consists in ionic compounds, in which the structural stability simply relies on electrostatic forces and weak intermolecular interactions between the different components. Indeed, the first crystal structure involving metalorganic complex moieties covalently grafted at the surface of decavanadate anions was not reported until 2007, and almost all compounds with such characteristics that have been prepared later consist in either discrete decorated clusters or mono-dimensional arrangements . To our knowledge, only two decavanadate/metalorganic hybrid lattices with covalent bi-dimensional nature can be found in the literature, namely, (Hpz) 2 ­[{Cu­(pz) 4 } 2 ­(V 10 O 28 )]·2H 2 O (pz = pyrazole) and [{Ag 3 (DMSO) 6 }­{Ag­(DMSO) 2 }­(H 2 V 10 O 28 )]·2DMSO (DMSO = dimethyl sulfoxide).…”

Proton conductivity resulting from different triazole-based ligands in two new bifunctional decavanadates

“…S1a † ), and the V–O bond distances vary from 1.610(8) to 2.302(8) Å, which are similar to those of the reported decavanadate structure. 11 There are two crystallographically independent Zn ions (Zn1 and Zn2) in compound 1. Zn2 is six-coordinated by three N atoms from the ligands and three O atoms from the water molecules.…”

Recent advances in oxidative catalytic applications of polyoxovanadate-based inorganic–organic hybrids

“…Recently, POVH materials were employed in electrocatalytic reduction of iodate, 65 hydrogen peroxide 67 and reduction or oxidation of nitrite, 68–70 due to their ability to undergo a series of reversible multi-electron redox processes. Compared with the electrocatalytic reduction activity, the electrooxidative catalytic activity of POVH materials was rarely explored, especially toward the oxidative transformation of organic molecules.…”