Successive constructions of regular tetra-, hexa- and octanuclear microporous polyoxovanadates(iii) for gas adsorption

Abstract

Pyrazole-assisted tetranuclear microporous polyoxovanadates(III) (POVs) (NH₄)₂K₂[V₄(μ₂-OH)₄(ox)₄(pz)₄]·9H₂O (1, ox = oxalate and pz = pyrazole) and (NH₄)₂Na₂[V₄(μ₂-OH)₄(ox)₄(4-mpz)₄]·7H₂O (2, 4-mpz = 4-methylpyrazole) have been constructed in reduced media, along with their triazole neutral hexa- and octanuclear products K₂[V₆(μ₂-OH)₆(ox)₆(Hdatrz)₆]Cl₂·29.5H₂O (3) and [V₈(μ₂-OH)₈(SO₃)₈(Hdatrz)₈]·38H₂O (4, Hdatrz = 1H-1,2,4-triazole-3,5-diamine) successively. Both polyanionic structures of 1 and 2 share similar inorganic building blocks that consist of regular {V₄(μ₂-OH)₄} skeletons with an inner diameter of 2.8 Å, while a paddle wheel-shaped cluster 3 contains a {V₆(μ₂-OH)₆} skeleton with two chlorides encapsulated around the center of the ring, occupying a hole of 3.7 Å. An interesting isolated intrinsic polyoxometalate-based metal–organic framework (POMOF) 4 exists as an octanuclear petaloid-like skeleton {V₈(μ₂-OH)₈(SO₃)₈} with an inner diameter of 5.2 Å. Bond valence sum calculations manifest that all V ions have severely reduced +3 oxidation states in 1–4, which are supported by charge balance, structural and magnetic data. Moreover, gas adsorptions indicate that 1, 2 and 4 can adsorb CO₂ and O₂ more favorably than N₂, CH₄ and H₂ gases. Compared with 1 and 2, due to the functionalization of microchannels with Lewis base amino and hydroxy groups and uncoordinated azolate N-donors inside POMOF 4, it should have notable affinities toward CO₂ adsorption.