Syntheses, Structures And Luminescent Properties Of New Organic-Inorganic Coordination Polymers Generated From Fulvene And Schiff-base Ligands

The chemistry of organic-inorganic coordination polymers has recently become area of increasing interest. Self-assembly of organic ligands and inorganic metal ions is one of the most efficient and widely used approaches for the construction of organic-inorganic composite materials. In this paper, we wish to report the syntheses, structures and luminescent properties of 11 new organic-inorganic coordination polymers generated from fulvene ligands or Schiff-base ligandsA. Synthesis of fulvene ligands and their coordination chemistryNew type of fulvene ligands L1-L18 were synthesized by substituted-benzoyl chloride with Cp and subsitituted Cp anions and Heck-coupling reactions. Their coordination chemistry with "soft" Ag(I) metal ion and was also investigated. Three new fulvene polymeric compounds, namely 1([Ag (L3)]CH2C12 ), 2([Ag2(L25)(H2O)(S03CF3)2]0.5C6H6) and 3 (Mn(L4)2(C2H5OH)2) , were synthesized, respectively. Compounds 1 and 2 reported herein represent the organometallic polymers based on both Ag-N and Ag-C coordination interactions. In the solid state, compound 3 are bound together by strong intermolecular N H-O hydrogen bonding system into a supramolecular one-dimensional H-bonded chain.B. The coordination chemistry of Schiff-base ligandsThe coordination chemistry of Schiff-base ligands, namely 2,5-bis(3-methylpyrazinyl)-3,4-diaza-2,4-hexadiene (L19) and2,5-bis(pyrazinyl)-3,4-diaza-2,4-hexadiene (L20), with Ag(I) salts has been investigated. Coordination polymers [Ag(L19)]ClO4-0.5CH3OH(4), [Ag(L19)]PF60.5CH3OH(5), [Ag(L19)]SbF60.5CH3OH(6),[Ag(-L19)](BF40.5CH3OH(7), [Ag4(L20)4](PF6)4-CHCl3(8),Ag2(L20)2](SbF6)2-CH2Cl2(9), [Ag5(L20)3(NO3)3][Ag(NO3)3]-3CHCl3(10)and [Ag(L26)](SO3CF3) (11) were synthesized by combination of ligands L19-L20 with AgClO4H2O,AgPF6,AgSbF6,AgBF4,AgNO3,AgOTf, respectively. These 8 new compounds were fully characterized by IR, elemental analysis, TGA-DTA and single-crystal X-ray diffraction.C. The luminescent properties of organic ligands L3, L25, L19, L20 and also polymeric compounds (1-10) were investigated in the solid state. The results have shown that the emission colors and intensity of free organic molecules were significantly affected by their incorporation into the metal -containing polymeric compounds. The results reported herein demonstrate that the use of fulvene-type orSchiff-base organic spacers as precursors to bind transition metal ions, is in fact anew approach for the formation of novel supramolecular networks with interestingphysical properties.