Molecular and Polymeric Hybrids Based on Covalently Linked Polyoxometalates and Transition‐Metal Complexes

Abstract

A rational building‐block approach was employed to construct organometallic/polyoxometalate (POM) hybrids in which POM clusters and transition‐metal complexes are linked by a π‐conjugated bridge. The synthetic strategy for molecular and polymeric hybrids—POM functionalization with iodo‐bearing groups, attachment of a terpyridine‐type ligand, and metal coordination—is shown schematically in the picture.

Characterization, non-isothermal decomposition kinetics and photocatalytic water splitting of green chemically synthesized polyoxoanions of molybdenum containing phosphorus as hetero atom

“…Some structural details of molybdenum blue were elucidated by the solid state studies of Müller and associates [23,24]. Great breakthroughs have only been made in recent years with the discovery of self-assembling giant polyoxomolybdates (Mo-POM), such as "giant wheels" [25] and 11"keplerates" [26][27][28]. The spherical "keplerate" Mo-POMs have unique values among the MoPOMs discovered so far, owing to their sizes, structural complexity and striking aesthetic beauty [27].…”

Quantum Chemical Design for Enhanced Second‐Order NLO Response of Terpyridine‐Substituted Hexamolybdates

“…[18][19][20][21] POMs have been found to be extremely versatile inorganic building blocks for constructing functionally active materials, and POM-based organic-inorganic hybrid compounds are the combination of POMs with organic ligands. [22][23][24][25][26] Several reasons make these hybrids excellent candidates for novel NLO materials. Firstly, they offer a wide range of metals with different coordination states and various organic groups which possess large π-conjugated systems.…”

“…[22] Last but not least, POMs have been found to be extremely flexible building blocks as the non-centrosymmetric molecular structures can be achieved easily for such compounds. [22][23][24][25][26][27][28][29] In the present work, we have designed different sorts of molecular systems by introducing various electron acceptors at the end of the terpyridine ligand. We performed TDDFT analysis on the terpyridine derivatives of hexamolybdates and have calculated remarkably enhanced first hyperpolarizabilities (second-order polarizabilities).…”

Asymmetrical modification of Wells–Dawson POMs by Cu–phnz coordination polymers

“…Of particular importance is the addition of transition-metal ions onto the cluster surface, which even can result in the formation of novel metal-oxo frameworks [16][17][18]. Recently, plentiful amount of modifying POMs have been reported by Zubieta, Pope, Wang, Long, and Niu, and so on [19][20][21][22][23].…”