Hybrid vanadates constructed from extended metal–organic arrays: crystal architectures and properties

Abstract

Classification of inorganic–organic vanadates constructed from bridging ligands based on the metal–organic and inorganic substructures dimensionalities.

In Situ Ligand-Transformation-Involved Synthesis of Inorganic–Organic Hybrid Polyoxovanadates as Efficient Heterogeneous Catalysts for the Selective Oxidation of Sulfides

“…A universal pathway is to introduce the organic ligands into the reaction system to construct POV-based hybrids. Up to now, a large number of presynthesized organic ligands have been involved in the structures of POV-based hybrids, including not only bidentate nitrogen-donor ligands such as 1,2-di­(4-pyridyl)­ethylene and 1,4-bis­(imidazol-1-yl)­butane as well as multidentate such as 2,4,6-tri­(4-pyridyl)-1,3,5-triazine and so on, which have been summarized well in the review organized by Arriortua in 2014, but also many carboxylic acid ligands, − with the addition of those combining the nitrogen-donor group and carboxylic acid. , It should be pointed out that most organic ligands in these works are presynthesized and used directly, which prompts us to continue to design and develop more presynthesized organic ligands for exploiting POV-based hybrids with various structures.…”

Controllable Synthesis, Characterization, and Catalytic Properties of Three Inorganic–Organic Hybrid Copper Vanadates in the Highly Selective Oxidation of Sulfides and Alcohols

“…It is well-known that vanadium-based materials are active heterogeneous catalysts for several reactions but remain unexplored to a great degree . To our knowledge, only a few researches focused on the catalytic properties of inorganic–organic hybrid vanadates in the field of the oxidation sulfides, the cyanosilylation reaction of aldehydes with trimethylsilyl cyanide, the decomposition of methylene blue, splitting of water, and degradation of pollutants . The hybrid vanadates used in these catalytic reactions are the family of M­(HAep) 2 ­(VO 3 ) 4 (M = Co, Ni, Cu; Aep = 1-(2-aminoethl)­piperazine) compounds, [{CoNi­(H 2 O) 2 ­(Bpe) 2 }­(V 4 O 12 )]·4H 2 O·Bpe, [{Ag­(Bpy)} 4 ­(V 4 O 12 )]·2H 2 O, [{Ag­(Dpa)} 4 ­(V 4 O 12 )]·4H 2 O and {Ag 4 (2-Pzc) 2 }­(V 2 O 6 ) (Bpy = 4,4′-bipyridine; Dpa = 1,2-bis­(4-pyridyl)-ethane; Pzc = pyrazine­carboxylate), [Ag­(Bbi)]­[{Ag­(Bbi)} 4 ­{Ag 3 (V 4 O 12 ) 2 }]·2H 2 O (Bbi = 1,4-bis­( N -imidazolyl)­butane), and Mn­(Bpy)­(V 4 O 11 )­(Bpy) .…”

Manganese–Vanadate Hybrids: Impact of Organic Ligands on Their Structures, Thermal Stabilities, Optical Properties, and Photocatalytic Activities

“…Vanadate/organic hybrid compounds have been of particular interest owing to the optical and photocatalytic properties of the related condensed vanadates, for example, BiVO 4 , Ag 3 VO 4 , and InVO 4 , which are reportedly active for dye degradation and water splitting when irradiated at visible-light wavelengths. − The vanadate hybrid compounds have yielded a number of closely related structures containing extended homometallic [−O–V–O–V–O−] n and heterometallic [−O–V–O–M–O−] n (M = Ag, Cu, Mn) connectivity, as reviewed previously. a, Recently reported examples include Ag 4 (pzc) 2 V 2 O 6 (pzc = pyrazine-2-carboxylate), Co­(bimb)­V 2 O 6 (bimb = 1,3-bis­(1-imidazolyl)­benzene), and Mn­(2,2′-bpy)­V 4 O 10 (2,2′-bpy), as well as others. , In each of these cases the fundamental bandgap transition originates from a metal-to-metal charge transfer transition, that is, between the filled Ag 4d 10 and empty V 3d 0 orbitals in Ag 4 (pzc) 2 V 2 O 6 . Importantly, their bandgap sizes fall within the visible-light wavelengths, thus facilitating their potential use with the solar spectrum to drive photocatalytic reactions for either water purification or hydrogen production. , The relatively few examples reported so far have already enabled a beginning understanding of the structural and electronic origins of their photocatalytic activities when irradiated in aqueous solutions.…”