Hydrothermal synthesis and characterization of two novel tungstovanadophosphate derivatives

Abstract

Two novel tungstovanadophosphate derivatives, namely [Fe(phen) 3 ] 2 [PW 8 VI V V V 5 IV O 42 ] Á H 2 O (1) and [Fe(phen) 3 ] 2 [PW 9 V 3 O 40 ] (2), were synthesized under hydrothermal conditions, and characterized by elemental analysis, IR, ESR, XPS, TGA, and single-crystal X-ray diffraction analysis. The crystal structure analyses reveal that the 'mixed-addenda' Keggin polyoxoanion in 1 is decorated with VO 2+ units, such that four V atoms are disordered over eight metal sites; the anion in compound 2 has a typical Keggin structure with three V atoms disordered over 12 metal sites. The two compounds are ionic crystals with slightly different packing modes for the polyoxoanions and [Fe(phen) 3 ] 3+ cations. p-p stacking interactions between phen molecules, weak hydrogen bonding interactions between phen ligands and polyoxoanions, and electrostatic forces lead to an extended 3D supramolecular framework.

Crystal structure of hexakis(dimethylsulfoxide-κO)iron(III)dodecatungstophosphate, C12H36FeO46PS6W12

“…Interestingly the combination of iron(III)c omplexes of oxygen containing solvents with polyoxotungstenate was not achieved yet, while four examples exist of Fe 3+ complexes with N-containing ligands and polyoxotungstenate [3][4][5][6] 12 O 40 ], whose asymmetric unit consists of half ap olyanion and half ac omplex. The polyanion shows adisorder in the centre, which is commonly observed for the Keggin-anion [7,8].…”

Two New Compounds Based on Bi-Capped Keggin Polyoxoanions and Cu-Bpy Cations Contain Both CuII and CuI Complexes: Synthesis, Characterization and Properties

“…As one of the fundamental polyanions, the Keggin POMs anions have gained much attention, and a variety of structures composed of “substituted Keggin polyanions” [ 36 , 37 , 38 , 39 , 40 , 41 ], “capped Keggin polyanions” [ 42 , 43 , 44 , 45 ] and “substituted and capped Keggin polyanions” [ 46 , 47 , 48 , 49 , 50 , 51 , 52 ] have been reported, in which Keggin-type POMs anions are also regarded as the most desirable building blocks for the construction of inorganic–organic hybrid materials attributed to its intrinsic nonlinear optics, thermal stability, diverse electrons, redox properties, and so on [ 53 , 54 , 55 , 56 ]. Up to now, a new advancement has produced plenty of fascinating structures and better-performing hybrid materials passing through the intelligent selection between capped Keggin-type POMs and TMCs, and more researchers are devoted to the study of POM-TMC materials.…”

Supramolecular Networks Extended by N–H···O Interactions between Cu‐Benzimidazole Subunits and Keggin Anions

“…Among these donors, discrete metal‐organic subunits combine the geometric design and interactional features of metal cations and organic ligands, including the geometric requirements of the metal cation, the metal‐binding mode of the ligand, and the positioning and nature of the additional functional groups on the ligand backbone 10. For example, some metal‐organic subunits as hydrogen bonding donors derived from 2, 2′‐bipyridine and 1, 10′‐phenanthroline were prepared by Chen's and Ali's groups 11,12. In these reports, only weak C–H ··· O hydrogen bonding interactions were observed between the metal‐organic donors and POM acceptors.…”