Two Organic-Inorganic Hybrid 3D {P_5W_(30)}-Based Heteropolyoxotungstates with Transition-Metal/Ln-Carboxylate-Ln Connectors

摘要

Two unique organic-inorganic hybrid polyoxometalates constructed from Preyssler-type [Na(H_2O)-P_5W_(30)O_(110)]~(14-) ({P_5W_(30)}) subunits and TM/Ln-carboxylate-Ln connectors (TM=transition metal, Ln=lanthanide), KNa_7[{Sm_6Mn(μ-H_2O)_2(OCH_2-COO)_7(H_2O)_(18)}{Na(H_2O)P_5W_(30)O_(110)}]-·22H_2O (1) and K_4[{Sm_4Cu_2(gly)_2(ox)-(H_2O)_(24)}{NaP_5W_(30)O_(110)}]Cl_2·25H_2O (2; gly=glycine, ox=oxalate) have been hydrothermally synthesized and characterized by elemental analyses, IR spectra, UV/Vis-NIR spectra, thermogravimetric analyses, power X-ray diffraction, and single-crystal X-ray diffraction. Compound 1 displays one interesting 3D framework built by three types of subunits, {P_5W_(30)}, [Sm_2Mn(μ-H_2O)_2(OCH_2COO)_2(H_2O)_5]~(4+), and [Sm_4(OCH_2COO)_5 (H_2O)_(13)]~(2+), whereas 2 also manifests the other intriguing 3D architecture created by three types of subunits, {P_5W_(30)}, [SmCu(gly)-(H_2O)_8]~(4+), and [Sm_2(ox)(H_2O)_8]~(4+). To our knowledge, 1 and 2 are the first 3D frameworks that contain {P_5W_(30)} units and TM/Ln-carboxylate-Ln connectors. The fluorescent properties of 1 and 2 have been investigated.