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摘要:
Sixteen lanthanide-diphosphate complexes [LnL(2)(H2O)(4)Cl] Cl-2 (Ln = La3+ for 1, Ln = Ce3+ for 2), [LnL(2)(H2O)(4)] Cl-3.6H(2)O (Ln = Nd3+ for 3, Ln = Sm3+ for 4, Ln = Eu3+ for 5, Ln = Gd3+ for 6, Ln = Tb3+ for 7, Ln = Dy3+ for 8, Ln = Er3+ for 9), {[LaL2(H2O)(4)Cl]Cl-2}(2) (10), [PrL2(OH)(2)(H2O)Cl] [PrL2(H2O)(4)Cl]Cl-2 (11), [LaL2(H2O)(5)Cl]Cl-2.2H(2)O (12), [YbL2(H2O)(3)Cl] Cl-2.H2O (13), [NdL2(H2O)(3)Cl]Cl-2.3H(2)O (14), [HoL2(H2O)Cl-2]Cl.H2O (15), [Sc2L2(H2O)(4)(OH)(2)]Cl-4.4H(2)O.2CH(3)OH (16) (L = tetrakis(O-isopropyl) methylenediphosphonate) have been synthesized by the reaction of lanthanide chlorides and L ligand in the solvent of acetonitrile (with ethanol or DMF) at room temperature. The title complexes were characterized by IR, elemental analysis, single-crystal X-ray diffraction analysis, thermal analysis, (HNMR)-H-1 and (PNMR)-P-31 spectroscopy. Complexes 1-15 are mononuclear complexes and complex 16 is a binuclear cluster complex. Complex 12 is the intermediate of complex 1. Complexes 11-13 display a one-dimensional chain formed by hydrogen bonds and the structures of complexes 14, 16 can be simplified as two-dimensional mesh 63 topology formed by hydrogen bonds. In those lanthanide complexes, the lanthanide ion with an atomic number smaller than Pr element tends to form a nine-coordinated structure and that with the atomic number larger than Pr element tends to form an eight or lower number-coordinated structure. Pr element has two kinds of coordination situations, with coordination numbers of nine or eight. The terahertz (THz) time-domain spectra of these complexes were also studied.
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