Three novel coordination polymers [Pb(bbbm)2(NO3)2]n (bbbm=1,1'-(1,4-butanediyl)bis-1H-benzimidazole) 1, [Zn(bbbt)(NCS)2]n (bbbt=1,1'-(1,4-butanediyl)bis-1H-benzotriazole) 2, and [Zn(pbbt)(NCS)2]n (pbbt=1,1'-(1,3- propylene)bis-1H-benzotriazole) 3 were synthesized and structurally characterized. Polymer 1 exhibits a two-dimensional rhombohedral grid network structure, the dimensions of the grid are 14.274×14.274 Å, and the diagonal-to-diagonal distances are 24.809×14.125 Å. Polymer 2 possesses a concavo-convex chain structure different from those of the known one-dimensional polymers, which are linear chain, zigzag chain, helical chain, double-stranded chain, and ladder chain. Polymer 3 exhibits a one-dimensional zigzag chain structure, and these chains were packed as an...ABAB... layered structure. The third-order nonlinear optical (NLO) properties of polymers 1, 2, and 3 were determined with a 7-ns pulsed laser at 532nm. 1 shows strong third-order NLO absorptive and refractive properties, and its R2 and n2 values were calculated to be 5.8×10-9m W-1 and 4.67×10-18m2 W-1 in a 3.4×10-4 mol dm-3 DMF solution, respectively. Both 2 and 3 exhibit weaker NLO absorption and strong refractive properties, and their n2 values are 4.53×10-18m2 W-1 for 2 in a 5.2×10-4 mol dm-3 DMF solution and 3.02×10-18m2 W-1 for 3 in a 4.35×10-4mol dm-3 DMF solution. The χ(3) values of 1, 2, and 3 were calculated to be 1.67×10-11, 1.62×10-11, and 1.08×10-11 esu, respectively, and the values are larger than those of the reported coordination polymers. We deduce that the valence shell structures of metal ions may have some influence on the strength of NLO properties, and discuss the relationships between the crystal structures of coordination polymers and the observed NLO properties.

Treatment of two kinds of ferrocenyl-substituted carboxylate ligands (3-ferrocenyl-2-crotonic acid, HOOC-CH=(CH3)CFc (Fc=(η5-C5H5)Fe(η5-C5H4)) or O-ferrocecarbonyl benzoic acid, o-HOOCC6H4COFc with Pb(OAc)2·3H2O, Zn(OAc)2·2H2O, or Cd(OAc)2·2H2O) resulted in four novel ferrocene-containing coordination polymers {[Pb(μ2-η2-OOCCHd(CH3)CFc)2]·MeOH}n (1), {[Zn(o-OOCC6H4COFc)2(4,4'-bipy)(H2O)2]·2MeOH·2H2O}n (4,4'-bipy) 4,4'-bipyridine) (2), {[Cd(o-OOCC6H4COFc)2(bpe)(MeOH)2]·2H2O}n (bpe=1,2-bis(4-pyridyl)ethene) (3), and [Pb(o-OOCC6H4COFc)(η2-o-OOCC6H4COFc)(bpe)]n (4). Their crystal structures have been characterized by single X-ray determinations. In polymer 1, Pb(Ⅱ) ions are bridged by tridentate FcC(CH3)dCHCOO- anions, forming an infinite chain [Pb(μ2-η2-OOCdCH(CH3)CFc)2]n. In polymers 2-4, there are three kinds of components, metal ions, o-FcCOC6H4COO- units, and organic bridging ligands. The bipyridine-based ligands connect metal ions leading to a one-dimensional chain with o-FcCOC6H4COO-units acting as monodentate or chelate ligands in the side chain. Such coordination polymers containing ferrocenyl-substituted carboxylate and bipyridine-based ligands are very rare. The solution-state differential pulse voltammetries of polymers 1-4 were determined. The results indicate that the half-wave potential of the ferrocenyl moieties is influenced by the Pb(Ⅱ) ions in polymer 1 and strongly influenced by Zn(Ⅱ), Cd(Ⅱ), or Pb(Ⅱ) ions in polymers 2-4. The thermal properties of the four polymers were also investigated.

Three novel ferrocenyl complexes [Zn(4-PFA)2(NO3)2](H2O) (1), [Hg2(OAc)4(4-BPFA)2](CH3OH) (2), and [Cd2(OAc)4-(4-BPFA)2] (3) (4-PFA=[(4-pyridylamino)carbonyl]ferrocene, 4-BPFA) 1,1'-bis[(4-pyridylamino)carbonyl]ferrocene) were prepared, and complexes 1 and 2 were structurally characterized by means of X-ray single-crystal diffraction. In complex 1, the zinc(Ⅱ) atom is coordinated at a distorted tetrahedral environment by two nitrogen atoms from two 4-PFA moieties and two oxygen atoms from two nitrate anions; [Zn(4-PFA)2(NO3)2] units are linked by hydrogen bonds N-H…O and O-H…O forming one-dimensional chains. Complex 2 is a tetranuclear macrocycle compound consisting of two 4-BPFA moieties and two Hg atoms; [Hg2(OAc)4(4-BPFA)2] units form 1-D chains by hydrogen bonds N-H…O as complex 1. Some complexes with 1,1'-bisubstituted pyridine-containing ferrocene ligands have been described, but their crystal data are limited. Compound 2 is the first example of a macrocyclic pyridinecontainingferrocenyl complex. The third-order nonlinear optical (NLO) properties of 4-PFA, 4-BPFA, and complexes 1-3 were determined by Z-scan techniques. The results indicate that all the compounds exhibit strong self-focusing effect. The hyperpolarizability ç values are calculated to be in the range 1.51×10-28 to 3.12×10-28 esu. The γ values are nearly twice as large for complexes 1-3 as for their individual ligands, showing that the optical nonlinearity of the complexes is dominated by the ligands.

A new bidentate "building block", N,N'-bis(3-pyridylformyl)piperazine (bpfp), was synthesized.X-ray diffraction studies reveal that the piperazine ring in bpfp forms a chairlike structure conformation. bpfp self-assembled into two-dimensional layered rhombohedral grid polymers {[Mn(H2O)2-(SO4)(bpfp)](H2O)3(CH3OH)}n (1) and {[Zn(NCS)2(bpfp)2]·2H2O}n (2) with Mn(Ⅱ) and Zn(Ⅱ), a threedimensional polymer [Cd(N3)2(bpfp)]n (3) with Cd(Ⅱ), and a one-dimensional zigzag polymer [HgI2(bpfp)]n (4) with Hg(II). Each rhombohedral grid in polymer 1 is composed of four Mn, two bpfp, and two SO4 2-; the dimensions of the grid are 6.537×12.843 Å. In polymer 2, each rhombohedral grid consists of 60-membered rings Zn4(bpfp)4 showing the dimensions of 14.231×15.586 Å. Zn4(bpfp)4 grids are bridged by Zn ions and all pyridyl-N atoms of bpfp ligands into the 2-D network structure along a and c directions. Polymer 3 exhibits a 3-D layered structure with tetragonal prism channel viewing from a direction. The bpfp ligands occupy the four edges of tetragonal prism channel, which is cut off by layers consisting of rhombohedral grids Cd4(N3)4. Polymer 4 is quite different from polymers 1-3; it exhibits a 1-D zigzag framework extending along the c axis. Polymers 1-3 possess a very strong NLO absorption and selffocusing effect. Their third-order NLO absorptive coefficients R2 are 9.2×10-9, 6.9×10-9, and 7.1×10-9mW-1. The third-order NLO hyperpolarizabilities γ are 1.79×10-28, 9.10×10-29, and 9.66×10-29 esu, respectively. The γ values are comparable to those of the best NLO materials and coordination polymers. We found that the valence shell structures of central metal ions can influence the NLO properties of coordination polymers.

Using FcCOONa (Fc=η5-C5H5)Fe(η5-C5H4)) as starting material, we obtained an unprecedented metal-organic coordination polymer containing ferrocenecarboxylate components {[Pb2(FcCOO)(η2-FcCOO)(μ2-η2-FcCOO)(μ3-η2-FcCOO)(CH3OH)]·1.5CH3OH·H2O}n (1), tetramer [Zn4(μ2-FcCOO)6(μ4-O)] (2), and coordination polymers [Pb-(FcCOO)(μ2-FcCOO)(bpe)]n (3) (bpe) 1,2-bis(4-pyridyl)ethene), {[Zn(FcCOO)2(bpt)]·2.5H2O}n (4) (bpt ) N,N'-bis(3-pyridylmethyl)thiourea), and [Zn(FcCOO)(η2-FcCOO)(bbp)]n (5) (bbp ) 4,4'-trimethylene-dipyridine). Compounds 1 and 2 are formed by ferrocenecarboxylate units coordinating with Pb(Ⅱ) or Zn(Ⅱ). In polymer 1, ferrocenecarboxylate units have four kinds of coordinate modes; just these novel coordinate modes lead to the unprecedented onedimensional polymer where two kinds of rhomboids are arranged alternatively along the chain. Compound 2 is a tetramer, in which a distinct connectivity of the six ferrocene units is established through the four Zn atoms. Compounds 3-5 are obtained by organic ligands bridging Pb(Ⅱ) or Zn(Ⅱ), leading to a new type of metal-organic coordination polymer.