Two new bent bis(cyanophenyl)oxadiazole ligands, 2,5-bis(4-cyanophenyl)-1,3,4-oxadiazole (L7) and 2,5-bis(3-cyanophenyl)-1,3,4-oxadiazole (L8), were synthesized. The coordination chemistry of these ligands with various Ag(I) salts has been investigated. Seven new coordination polymers, namely, {[Ag(L7)(H2O)]ClO4}n (1) (triclinic, P1h, a=9.342(4) Å, b=9.889(4) Å, c=10.512(4) Å, R=68.978(6)°, β=78.217(6)°, ç=81.851(7)°, Z=2), {[Ag(L7)]SO3CF3}n (2) (monoclinic, P21/n, a=7.559(2) Å, b=23.739(6) Å, c=10.426(3) Å, β=108.071(4)°, Z=4), {[Ag(L8)]BF4β0.5(C6H6)βH2O}n(3) (triclinic, P1h, a=7.498(3) Å, b=10.649(4) Å, c=13.673(5) Å, R=98.602(5)°, β=100.004(5)°, ç )110.232(5)°, Z=2), {[Ag(L8)SbF6]βH2O}n (4) (triclinic, P1h, a=8.2621(9) Å, b=10.6127(12) Å, c=13.3685(15) Å, R=98.012(2)°, β=106.259(2)°, ç=112.362(2)°, Z=2), {[Ag2(L8)2(SO3CF3)]βH2O}n (5) (triclinic, P1h, a=10.713(4) Å, b=13.449(5) Å, c=15.423(5) Å, R) 65.908(5)°, β=74.231(5)°, ç=83.255(5)°, Z=2), {[Ag2(L8)(C6H6)(ClO4)]βClO4}n (6) (monoclinic, P21/n, a=6.9681(17) Å, b=20.627(5) Å, c=17.437(4) Å, β=95.880(4)°, Z=4), and {[Ag2(L8)(H2PO4)2]}n (7) (triclinic, P1h, a=7.956(2) Å, b=9.938(3) Å, c=14.242(4) Å, R=106.191(4)°, β=97.322(4)°, ç=107.392(4)°, Z=1), were obtained by the combination of L7 and L8 with Ag(I) salts in a benzene/methylene chloride mixedsolvent system and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the luminescence and electrical conductance properties of compounds 1-6 and the host-guest chemistry of compound 3 were investigated.

One new conjugated symmetric fulvene ligand L1 and two new unsymmetric fulvene ligands L2 and L3 were synthesized. Five new supramolecular complexes, namely Ag2(L1)3(SO3CF3)3 (1) (1, monoclinic, P21/c; a=12.702(3) Å, b=26.118(7) Å, c=13.998(4) Å, β=96.063(4)°, Z=4), [Ag(L1)]ClO4 (2) (monoclinic, C2/c; a=17.363(2) Å, b=13.2794(18) Å, c=13.4884(18) Å, β=100.292(2)°, Z=8), [Ag(L1)(C6H6)SbF6]β0.5C6H6βH2O (3) (monoclinic, P21/c; a=6.8839(11) Å, b=20.242(3) Å, c=18.934(3) Å, β=91.994(3)°, Z=4), Ag(L2)(SO3CF3) (4) (triclinic, P1h; a=8.629(3) Å, b=10.915(3) Å, c=11.178(3) Å,R)100.978(4)°, β=91.994(3)°, ç=105.652(4)°, Z=2), and Ag(L3)(H2O)(SO3CF3) (5) (triclinic, P1h; a=8.914(5) Å, b=10.809(6) Å, c=11.283(6) Å, R )69.255(8)°, β=87.163(9)°, ç=84.993(8)°, Z=2) were obtained through self-assembly based on these three new fulvene ligands in a benzene/toluene mixed-solvent system. Compounds 1-5 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can adopt either cis- or trans-conformation to bind soft acid Ag(I) ion through not only the terminal -CN and furan functional groups but also the fulvene carbon atoms into organometallic coordination polymers or discrete complexes. In addition, the luminescent properties of L1-L3 and their Ag(I) complexes were investigated preliminarily in EtOH and solid state.

Three new rigid conjugated fulvene ligands L1-L3 were synthesized. L1 and L3 have been prepared by an aroylation reaction of cyclohexyl-substituted cyclopentadienyl anions. L2 was prepared by the reaction of L1 with PhNHNH2 in hot enthanol. Six new coordination polymers, namely [Ag(C25H20N2O2)(ClO4)]β3.5C6H6 (1), [Ag2(í-C31H24N4)(è2-C6H6)(H2O)](ClO4)2β(C6H6)β(H2O)0.5 (3), [Ag(C31H24N4)]SbF6βsolvate (4), [Ag(C31H24N4)](SbF6)2β2C6H6βCH2Cl2 (5), [Ag-(C25H20N2O2)2]SbF6 (6), and [Ag(C25H20N2O2)2]SbF6 (7), and one seven-membered cobaltacycle-containing complex, namely Co(C25H20N2O2)2(C2H5OH)2 (2), were obtained through self-assembly based on these three new fulvene lignads. L2-L3 and compounds 1-7 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can bind metal ions not only through the terminal N-donors and fulvene carbon atoms into organometallic coordination polymers but also through the two chelating carbonyl groups into unusual sevenmembered metallo-ring supramolecular complexes. In the solid state, ligands L1-L3 are luminescent. A blue-shift in the emission was observed between the free ligand L1 and the one incorporated into Co(II)-containing complex 2, and a red-shift in the emission was observed between the free ligand L3 and the one incorporated into Ag(I)-containing polymeric ompounds 6 and 7.

Two new fulvene ligands, L1 and L2, have been synthesized by an aroylation reaction of the cyclopentadienyl anion. The coordination chemistry of L1 and L2 was investigated. Two novel CpAg(I)-containing polymeric compounds, 1 ([Ag4(L1)2(í-H2O)2(SO3CF3)4]β(í-bis-è1-C6H6))βH2O) and 2 ([Ag2(L2)(H2O)(SO3CF3)2]β0.5(C6H6)), have been synthesized. Compounds 1 and 2 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The solid state structure of 1 features a macro-ring-containing one-dimensional chain motif. The solid state structure of 2 features a one-dimensional doublechain motif. These double chains are further cross-linked to each other via CpAg(SO3CF3)2-AgCp (AgβββAg contact of 4.215(15) Å) linkage into a novel 2-D network with large cavities (effective cross-section of ca. 21 9 Å), in which the benzene guest molecules are located.

Two novel organic–inorganic hybrid coordination polymers were synthesized based on a new multidentate Schiff-base ligand and Ag(I) salts