Structural characterizations and magnetic properties of three new reduced molybdenum phosphates

Three new molybdophosphates, [Co(dien) 2]·(H 3dien) 6·{[CoMo 12O 24(OH) 6(HPO 4) 2(PO 4) 6][Co(Hdien)] 2[CoMo 12O 24(OH) 6(PO 4) 8]}·(dien)·4H 3O·5H 2O ( 1), (H 3dien) 4[ MMo 12O 24(OH) 6(HPO 4) 4(PO 4) 4]·10H 2O [ M=Co for ( 2), Ni for ( 3); dien=diethylenetriamine], have been synthesized by employing hydrothermal method and characterized by single crystal X-ray diffraction. Compound 1 is built up of Co[P 4Mo 6] 2 units as the structural motif covalently linked by [Co(Hdien)] complex subunits to yield an unusual 1-D chain. Compounds 2 and 3 are isomorphic and both display covalent discrete M[P 4Mo 6] 2 cluster structures which are linked by the hydrogen bonds to form 3-D supramolecular networks. Both 1 and 2 display antiferromagnetic interaction and these three compounds all exhibit intensive photoluminescence. Three new reduced molybdophoshpates based on P 4MO 6 building blocks have been hydrothermally synthesized. 1 is the first covalent 1-D chain consisting of two kinds of forms of M[P 4MO 6] 2 units, standing forms A and lying forms B, while 2 and 3 possess 3-D supramolecular network structures. These three compounds all display photoluminescence.