Nucleation Roadmap of Reduced Polyoxovanadate-Alkoxide Clusters

Overview

Journal Inorg Chem

Specialty Chemistry

Date 2025 Feb 20

PMID 39973095

Authors

S Genevieve Duggan

S M Gulam Rabbani

Pere Miro

Affiliations

Soon will be listed here.

Abstract

Polyoxovanadate-alkoxides are a growing family of earth-abundant first-row transition metal polynuclear species highly promising for their tunable redox properties. The speciation and nucleation chemical space of these species is divided into two groups: 1) fully oxidized V(V) monomeric precursors that aggregate into Lindqvist-type clusters and 2) reduced V(IV) precursors forming cyclic structures. The nucleation of cyclic polyoxovanadate-alkoxides with varying alkyl chain lengths, the impact of the presence of templating anions, and their subsequent evolution to the Lindqvist-type congener were studied by using density functional theory. The evolution of cyclic polyoxovanadate-alkoxides to oxygen-vacant cluster structures was found to be endergonic, in agreement with previous experimental work. Moreover, the reactivity with traces of water in alcohol solvents was confirmed to be the main thermodynamic driving force toward the formation of the mixed-valent Lindqvist-type polyoxovanadate species.

References

Monakhov K, Bensch W, Kogerler P . Semimetal-functionalised polyoxovanadates. Chem Soc Rev. 2015; 44(23):8443-83. DOI: 10.1039/c5cs00531k. View

Cooney S, Fertig A, Buisch M, Brennessel W, Matson E . Coordination-induced bond weakening of water at the surface of an oxygen-deficient polyoxovanadate cluster. Chem Sci. 2022; 13(43):12726-12737. PMC: 9645371. DOI: 10.1039/d2sc04843d. View

Petrus E, Segado-Centellas M, Bo C . Computational Prediction of Speciation Diagrams and Nucleation Mechanisms: Molecular Vanadium, Niobium, and Tantalum Oxide Nanoclusters in Solution. Inorg Chem. 2022; 61(35):13708-13718. DOI: 10.1021/acs.inorgchem.2c00925. View

Lee , Yang , PARR . Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B Condens Matter. 1988; 37(2):785-789. DOI: 10.1103/physrevb.37.785. View

Pappas I, Chirik P . Ammonia synthesis by hydrogenolysis of titanium-nitrogen bonds using proton coupled electron transfer. J Am Chem Soc. 2015; 137(10):3498-501. DOI: 10.1021/jacs.5b01047. View

Hu P, Hu P, Vu T, Li M, Wang S, Ke Y . Vanadium Oxide: Phase Diagrams, Structures, Synthesis, and Applications. Chem Rev. 2023; 123(8):4353-4415. PMC: 10141335. DOI: 10.1021/acs.chemrev.2c00546. View

Amanchi S, Das S . A Versatile Polyoxovanadate in Diverse Cation Matrices: A Supramolecular Perspective. Front Chem. 2018; 6:469. PMC: 6198037. DOI: 10.3389/fchem.2018.00469. View

Meyer R, Love R, Brennessel W, Matson E . Mechanistic insights into polyoxometalate self-assembly in organic solvent: conversion of a cyclic polyoxovanadate-ethoxide to its Lindqvist congener. Chem Commun (Camb). 2020; 56(61):8607-8610. DOI: 10.1039/d0cc03464a. View

Weigend F, Ahlrichs R . Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. Phys Chem Chem Phys. 2005; 7(18):3297-305. DOI: 10.1039/b508541a. View

10.

Vila-Nadal L, Mitchell S, Rodriguez-Fortea A, Miras H, Cronin L, Poblet J . Connecting theory with experiment to understand the initial nucleation steps of heteropolyoxometalate clusters. Phys Chem Chem Phys. 2011; 13(45):20136-45. DOI: 10.1039/c1cp21209e. View

11.

Perdew , Burke , Ernzerhof . Generalized Gradient Approximation Made Simple. Phys Rev Lett. 1996; 77(18):3865-3868. DOI: 10.1103/PhysRevLett.77.3865. View

12.

VanGelder L, Petel B, Nachtigall O, Martinez G, Brennessel W, Matson E . Organic Functionalization of Polyoxovanadate-Alkoxide Clusters: Improving the Solubility of Multimetallic Charge Carriers for Nonaqueous Redox Flow Batteries. ChemSusChem. 2018; 11(23):4139-4149. DOI: 10.1002/cssc.201802029. View

13.

Ribeiro R, Marenich A, Cramer C, Truhlar D . Use of solution-phase vibrational frequencies in continuum models for the free energy of solvation. J Phys Chem B. 2011; 115(49):14556-62. DOI: 10.1021/jp205508z. View

14.

Augustyniak-Jablokow M, Daniel C, Hartl H, Spandl J, Yablokov Y . Exchange interactions and electron delocalization in the mixed-valence cluster V(4)(IV)V(2)(V)O(7)(OC(2)H(5))(12). Inorg Chem. 2007; 47(1):322-32. DOI: 10.1021/ic7006974. View

15.

Petrus E, Buils J, Garay-Ruiz D, Segado-Centellas M, Bo C . POMSimulator: An open-source tool for predicting the aqueous speciation and self-assembly mechanisms of polyoxometalates. J Comput Chem. 2024; 45(26):2242-2250. DOI: 10.1002/jcc.27389. View

16.

Rabbani S, Miro P . Computational Insights into Iron Heterometal Installation in Polyoxovanadate-Alkoxide Clusters. Inorg Chem. 2022; 62(5):1797-1803. DOI: 10.1021/acs.inorgchem.1c03589. View

17.

Petrus E, Garay-Ruiz D, Reiher M, Bo C . Multi-Time-Scale Simulation of Complex Reactive Mixtures: How Do Polyoxometalates Form?. J Am Chem Soc. 2023; 145(34):18920-18930. DOI: 10.1021/jacs.3c05514. View

18.

Fertig A, Brennessel W, McKone J, Matson E . Concerted Multiproton-Multielectron Transfer for the Reduction of O to HO with a Polyoxovanadate Cluster. J Am Chem Soc. 2021; 143(38):15756-15768. DOI: 10.1021/jacs.1c07076. View

19.

Daniel C, Hartl H . Neutral and cationic V(IV)/V(V) mixed-valence alkoxo-polyoxovanadium clusters [V6O7(OR)12]n+ (R = -CH3, -C2H5): structural, cyclovoltammetric and IR-spectroscopic investigations on mixed valency in a hexanuclear core. J Am Chem Soc. 2005; 127(40):13978-87. DOI: 10.1021/ja052902b. View

20.

Anjass M, Lowe G, Streb C . Molecular Vanadium Oxides for Energy Conversion and Energy Storage: Current Trends and Emerging Opportunities. Angew Chem Int Ed Engl. 2020; 60(14):7522-7532. PMC: 8048609. DOI: 10.1002/anie.202010577. View