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.

Four novel cadmium-btx (btx=1,4-bis(triazol-1-ylmethyl)benzene) coordination polymers [Cd(btx)2(NO3)2]n (1), [Cd(btx)2Cl2]n (2), [Cd(btx)(SO4)(H2O)2]n (3), and [Cd(btx)(S2O7)(H2O)]n (4) have been prepared by hydrothermal reaction (140 or 180℃) and characterized. Both 1 and 2 have two-dimensional rhombohedral grid structures, 3 possesses a two-dimensional rectangular grid structure, and 4 displays a three-dimensional framework, which is formed by btx bridging parallel layers. To the author's best knowledge, polymer 4 is the first Cd(Ⅱ) polymer in which the Cd(Ⅱ) ion is eight-coordinated in a hexagonal bipyrimidal geometry. In addition, we studied the effects of temperature on the hydrothermal reaction system of btx and CdSO4 and found that different products can be obtained at different temperatures. Furthermore, polymer 3 possesses a very strong third-order NLO absorptive effect with an R2 value of 1.15×10-9m W-1. Polymers 2-4 display strong fluorescent emissions in the solid state at room temperature. The DTA and TGA results of the four polymers are in agreement with the crystal structures.

The ligand N,N'-bis(1,3,4-thiobiazolyl)-2,6-pyridyldicarboxamide (btapca) has been synthesized and its coordination properties toward La(Ⅲ) and Ce(Ⅲ) in the presence of air have been investigated. The complexes [Ln8(tbzcapc)12-(H2O)24]·6DMF (Ln=La, 1, Ce, 2; tbzcapc=6-[2-N-(1,3,4-thiabiazolyl)carboxamido]-2-pyridylcarboxylate) show octameric ellipsoid structures. We found the starting ligand btapca had been altered into tbzcapc during the formation process of [Ln8(tbzcapc)12(H2O)24]·6DMF. The NLO properties of complexes 1 and 2 were investigated via Z-scan techniques. It is interesting that the two isostructural complexes show completely different NLO properties. Complex 1 shows NLO refractive effects without absorption, while complex 2 possesses NLO absorptive behavior without refraction.

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.

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.