Treatment of p-ferrocenylbenzoate [p-HOOCH4C6Fc, Fc=(η5-C5H5)Fe(η5-C5H5)] with Mn(OAc)2·2H2O or Cd(OAc)2·2H2O afforded one-dimensional linear chain polymer {[Mn(OOCH4C6Fc)2(μ2-OH2)(H2O)2](H2O)}n (1), double-bridge polymer [Mn(μ2-OOCH4C6Fc)2(phen)]n (phen) phenanthroline) (2), and ladderlike framework {[Cd(μ2-OOCH4C6Fc)(η2-OOCH4C6Fc)(bbp)](CH3OH)}n (bbp=4,4'-trimethylene-dipyridine) (3). The solution-state cyclic voltammograms indicate that the half-wave potentials of the ferrocenyl moieties in these polymers are all shifted to positive potential compared to that of sodium p-ferrocenylbenzoate. Both 1 and 2 behave as 1D Heisenberg Mn(Ⅱ) chains with weak intrachain antiferromagnetic interactions between the local high-spin Mn(Ⅱ) ions, and the exchange coupling parameters J (-5.20 and -3.25cm-1 for 1 and 2, respectively) are larger than those of most of the reported di-Mn(Ⅱ) complexes that contain μ2-aqua and μ2-carboxylato units and one-dimensional Mn(Ⅱ) carboxylic polymers.

In this paper, treatment of 1,1'-(1,4-butanediyl) bis-1H-benzotriazole (bbbt) and KSCN with Co(Ⅱ), Mn(Ⅱ), or Cd(Ⅱ) afforded three two-dimensional rhombohedral grid coordination polymers [M(bbbt)2(NCS)2]n (M ) Co, 1; Mn, 2; Cd, 3). The two-dimensional rhombohedral grids are parallel to the crystallographic ac plane. The rhombohedral grid consists of 44-membered rings of M4(bbbt)4, and gives the dimensions of 12.913×10.764 Å for polymer 1, 13.106×10.797 Å for polymer 2, and 13.256×10.870 Å for polymer 3. The three polymers' third-order nonlinear optical (NLO) properties were determined by Z-scan technique in DMF solution. The results show that all three polymers show very large NLO absorption and strong NLO refraction properties. The third-order NLO absorptive coefficients R2 are 5.4×10-9m W-1 for polymer 1, 5.2×10-9m W-1 for polymer 2, and 5.0×10-9m W-1 for polymer 3. The R2 values are larger than those of all the reported cluster compounds. The NLO refractive index values n2 of the three polymers are 5.73×10-19, 3.55×10-19, and 3.07×10-19 m2 W-1, respectively. Their hyperpolarizability γ values are calculated to be 2.40×10-30 esu for polymer 1, 1.52×10-30 esu for polymer 2, and 1.50×10-30 esu for polymer 3. The γ values are comparable to those of clusters and better than those of organometallic compounds, semiconductors, and fullerene.

Three novel ferrocenecarboxylato-bridged lanthanide dimers [Gd2(μ2-OOCFc)2(OOCFc)4(MeOH)2(H2O)2]·2MeOH·2H2O (1) (Fc=η5-C5H5)Fe(η5-C5H4)), [Nd2(μ2-OOCFc)2(OOCFc)4(H2O)4]·2MeOHâH2O (2), and [Y2(μ2-OOCFc)2-(OOCFc)4(H2O)4]·2MeOH (3) have been synthesized and characterized by single-crystal X-ray crystallography. In each complex, two Ln(Ⅲ) (Ln=Gd, Nd, or Y) ions are bridged by two ferrocenecarboxylate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln2(μ2-OOCFc)2]; each Ln(Ⅲ) ion has an irregular polyhedral coordination environment with nine coordinated oxygen atoms derived from the ferrocenecarboxylate ligands and coordinated solvent molecules. In the solid-state structure of compound 1, [Gd2(μ2-OOCFc)2(OOCFc)4(MeOH)2(H2O)2] groups are joined together by hydrogen bonds forming a two-dimensional network. Both compounds 2 and 3 show onedimensional chain structures by hydrogen bonding; they are different from 1. Magnetic measurements show unexpected ferromagnetic coupling between the gadolinium(Ⅲ) ions; the best fittings to the experimental magnetic susceptibilities gave J=0.006cm-1 and g=2.0 for 1. The magnetic behavior for 2 was also studied in the temperature range of 1.8-300K.

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.

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.