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侯红卫, Gang Li, Hongwei Hou, * Linke Li, Xiangru Meng, Yaoting Fan, and Yu Zhu
Inorganic Chemistry, Vol. 42, No.16, 2003,-0001,():
-1年11月30日
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.
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侯红卫, Xiangru Meng, †, Yinglin Song, ‡, Hongwei Hou, *, Huayun Han, Bo Xiao, Yaoting Fan, and Yu Zhu†
Inorganic Chemistry, Vol. 43, No.11, 2004,-0001,():
-1年11月30日
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.
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侯红卫, Xiangru Meng, †, Yinglin Song, ‡, Hongwei Hou, *, Yaoting Fan, Gang Li, † and Yu Zhu†
Inorganic Chemistry, Vol. 42, No.4, 2003,-0001,():
-1年11月30日
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.
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侯红卫, Hongwei Hou, *, †, Yongli Wei, Yinglin Song, ‡, Yaoting Fan, † and Yu Zhu†
Inorganic Chemistry, Vol. 43, No.4, 2004,-0001,():
-1年11月30日
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.
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侯红卫, Hongwei Hou, * Linke Li, Gang Li, Yaoting Fan, and Yu Zhu
Inorganic Chemistry, Vol. 42, No.11, 2003,-0001,():
-1年11月30日
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.
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