Four chain-like hybrid compounds based on mixed carboxylic acid ligands-modified polyoxomolybdates,Co, Ni, Zn, Mn; Ala = alanine; PHBA = p-hydroxybenzonic acid), were prepared and characterized by elemental analysis, IR spectroscopy, solid diffuse reflective spectroscopy, TG analysis, powder X-ray diffraction, and single-crystal X-ray diffraction. Four isostructural compounds 1−4 not only represent the extended architectures constructed from two different organic ligands-modified polyoxometalates but also can rapidly catalyze the degradation of two chemical warfare agent simulants, 2-chloroethyl ethyl sulfide (CEES) and diethyl cyanophosphonate (DECP), at room temperature. The catalytic results were analyzed and confirmed by GC-FID, GC-MS, and 1 HNMR techniques. Within 5 min, CEES was high-selectively oxidized to the corresponding nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) using heterogeneous catalyst 1 with the oxidant H 2 O 2 (conversion % = 98.5%, selectivity % > 99.9%). FTIR, PXRD techniques, and the following cycles also ascertained the stability and structural integrity of 1 in the oxidation reaction. Within 10 min, DECP can be almost entirely hydrolyzed to the nontoxic products catalyzed by 1 (conversion % = 99.0%). To our knowledge, they are in the rank of highly active catalysts for the degradation of CEES and DECP to date, accompanied by the advantages of steady reuse.

Four new hybrid architectures containing a [CoMoHO] polyoxoanion, (en)[Cu(ptz)(HO)][CoMoHO]·24HO (1), (Hbim)[{Cu(bim)(HO)}{CoMoHO}]·5HO (2), H[Cu(dpdo)(HO)][{Cu(dpdo)(HO)(CHCN)}{CoMoHO}]·9HO (3), and (Hbpp)[{Cu(HO)}{NaCoMoHO}]·10HO (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [CoMoHO] as the guest. Compound 2 is constructed from [CoMoHO] polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [CoMoHO] polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [CoMoHO] polyoxoanions joined together by Na and Cu cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.

Twelve new hybrid dimers based on carboxylic acid ligand modified polyoxomolybdates were prepared, which can rapidly oxidize the mustard gas simulant, CEES, and hydrolyze the nerve agent simulant, DECP, at room temperature.

Herein, four hybrid dimers based on the carboxylic acid ligand-modified polyoxomolybdates were prepared, which could rapidly and selectively oxidize various phenyl sulfides and the sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES).