Syntheses, Structural Characterization Luminescent Properties Of Supramolecular Complexes Generated From New Type Of Conjugated Fulvene Ligand

The chemistry of organic-inorganic coordination polymers or supramolecular architectures 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. So far, among the many diverse efforts to find key factors in the development of polymeric compounds with novel structures and physical-chemical properties, the dominant synthetic strategy has been to select different organic ligands with specific geometry and functional groups. In the thesis, we wish to report the synthesis and structures of a series of new type rigid conjugated nanometer-sized fulvene ligands, and coordination polymeric compounds based on both metal-carbon and metal-heteroatom interactions and also H-bonded supramolecular architectures generated from this new type of fulvene ligands.Totally 17 new type of fulvene ligands have been synthesized by the reaction of substituted-benzoyl chloride with Cp and substituted Cp anions. All the new compounds are fully characterized by infrared spectroscopy, !H NMR and elemental analysis, as well as for 5 represenatives by single-crystal X-ray diffraction methods. The structure analysis reveals that this new type of ligand exists in the form of fulvene, the two aroyl groups on the Cp or substituted-Cp ring are adjacent, the enol hydrogen atom (the proton resonance as singlet in the range of 17.71-18.33 ppm) is hydrogen bonded to the neighbor carbonyl oxygen atom (IR (C=O) in the range of 1610?630cm"1) to form a hydrongen bonded seven-membered ring. In addition, the two aroyl rings are not in the same plane with the seven-membered ring.Two novel Ag-containing polymeric compounds, namely [Ag2(L|)(H20)2(SO3 CF3)2] ?0. 5C6H6 (18) and Ag^L.M^OMSOsCFjM V-C6H6) (19) have been successfully synthesized by combination of the fulvene-typed organic spacers with AgSC^CFa in the solution. To our knowledge, compounds 18 and 19 reported herein represent the first example of organic-inorganic composite polymers based on both Ag-N and Ag-C coordination interactions. In the solid state, compound 18 features a one-dimensional double chain motif. These double chains are further cross-linked into a two-dimensional network by stronginter-chain O....H-O hydrogen bonds. The two-dimensional network has remarkably large cavities (effective cross-section of ca. 21><15 A), in which the benzene guest molecules are located. A totally different polymeric pattern was found in compound 19. In the solid state, the supramolecular Ag-containing rings in 19 are connected to each other by benzene molecules with n '-coordination bonding model through two carbon atoms on /wt'.y0-positions into a novel one-dimensional chain. It is worthy pointing out that there are two types of Ag-C bonding models found in 19 including /7'-C6H6-Ag and /72-Cp-Ag.Three new H-bonded one-dimensional supramolecular compounds, namely M(C3oH2iN2O2)2(C2H5OH)2 (M - Cu(II) (20), Co(II) (21) and Mn(II) (22), were also synthesized by the reactions of metal (Cu2+, Co2+, Mn2+) acetate with this new type of fulvene ligand. Single-crystal structures reveals that these three molecular complexes are isostructural. A novel seven-membered metal-ring was found in 20-22. In the solid state, these neutral complexes as building blocks are bound together by strong intermolecular N---H-O hydrogen bonds into a supramolecular one-dimensional chain.The luminescent properties of polymeric compounds and also their fulvene ligands were investigated in the solid state. The results have shown that the emission wavelength and intensity of free organic molecules were affected by their incorporation into the Ag-containing polymeric compounds and transition metal complexes.