Two-dimensional rhombohedral grid coordination polymers [M(bbbt)(2)(NCS)(2)](n)(M = Co,Mn, or Cd; bbbt = 1,1'-(1,4-butanediyl) bis-1H-benzotriazole): synthesis,crystal structures,and third-order nonlinear optical properties

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 M(4)(bbbt)(4), and gives the dimensions of 12.913 x 10.764 A for polymer 1, 13.106 x 10.797 A for polymer 2, and 13.256 x 10.870 A 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 alpha(2) are 5.4 x 10(-9) m W(-1) for polymer 1, 5.2 x 10(-9) m W(-1) for polymer 2, and 5.0 x 10(-9) m W(-1) for polymer 3. The alpha(2) values are larger than those of all the reported cluster compounds. The NLO refractive index values n(2) of the three polymers are 5.73 x 10(-19), 3.55 x 10(-19), and 3.07 x 10(-19) m(2) W(-1), respectively. Their hyperpolarizability gamma values are calculated to be 2.40 x 10(-30) esu for polymer 1, 1.52 x 10(-30) esu for polymer 2, and 1.50 x 10(-30) esu for polymer 3. The gamma values are comparable to those of clusters and better than those of organometallic compounds, semiconductors, and fullerene.     

Novel pb and zn coordination polymers: synthesis,molecular structures,and third-order nonlinear optical properties

Three novel coordination polymers [Pb(bbbm)(2)(NO(3))(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 x 14.274 A, and the diagonal-to-diagonal distances are 24.809 x 14.125 A. 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 polymers1, 2, and 3 were determined with a 7-ns pulsed laser at 532 nm. 1 shows strong third-order NLO absorptive and refractive properties, and its alpha(2) and n(2) values were calculated to be 5.8 x 10(-)(9) m W(-)(1) and 4.67 x 10(-)(18) m(2) W(-)(1) in a 3.4 x 10(-)(4) mol dm(-)(3) DMF solution, respectively. Both 2 and 3 exhibit weaker NLO absorption and strong refractive properties, and their n(2) values are 4.53 x 10(-)(18) m(2) W(-)(1) for 2 in a 5.2 x 10(-)(4) mol dm(-)(3) DMF solution and 3.02 x 10(-)(18) m(2) W(-)(1) for 3 in a 4.35 x 10(-)(4) mol dm(-)(3) DMF solution. The chi((3)) values of 1, 2, and 3 were calculated to be 1.67 x 10(-)(11), 1.62 x 10(-)(11), and 1.08 x 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.     

A series of metal-organic polymers assembled from MCl2 (M = Zn, Cd, Co, Cu): structures, third-order nonlinear optical and fluorescent properties

In this paper four metal-organic polymers {[Zn(fcz)Cl2].CH3OH}n 1, {[Cd(fcz)2Cl2].CH3OH.2H2O}n 2, {[Co(fcz)2Cl2].2CH3OH}n 3 and {[Cu(fcz)2Cl2].2CH3OH}n 4 (fcz = fluconazole: alpha-(2,4-difluorophenyl)-alpha-(1H-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole-l-ethanol) were synthesized and characterized by X-ray single crystal diffraction. Polymer consists of 1-D infinite chains arranged along the b-axis. All of polymers 2-4 exhibit a 2-D rhombohedral grid structure. We study the third-order nonlinear optical properties of fcz and polymers 1-4 in DMF solution by using 8 ns laser pulses at 532 nm, and find that 1 and 4 exhibit different NLO properties from fcz and both 2 and 3 show similar NLO properties to fcz. 1 possesses strong NLO refractive effects and large NLO absorptive behaviors. 2, 3 and fcz exhibit strong refractive effects, but their NLO absorptive behaviors are weaker than that of 1. The NLO effects of 4 are very weak. The study of optical limiting (OL) effects by using 40 ps laser pulses at 532 nm shows that fcz and polymer 3 possess a strong OL effect. The optical limiting threshold values of 0.15 J cm(-2) for fcz and 0.16 J cm(-2) for are comparable to those of many heterothiometallate clusters. Polymers 1, 2 and 4 show a weak OL effect. The fluorescent spectra in DMF solution (concentration: 1 x 10(-4) mol dm(-3)) show that polymers 1-4 exhibit different luminescence properties from fcz. The maximum wavelength of polymers 1-3 are blue shifted gradually by 2-12 nm while polymer 4 exhibits a fluorescent self-quenching phenomenon. These results demonstrate that metal ions play an important part in the NLO and fluorescent properties of coordination polymers.     

1D + 1D → 1D polyrotaxane, 2D + 2D → 3D interpenetrated, and 3D self-penetrated divalent metal terephthalate bis(pyridylformyl)piperazine coordination polymers

Divalent metal coordination polymers containing terephthalate (tere) and bis(4-pyridylformyl)piperazine (bpfp) show diverse and interesting two-dimensional (2D) interpenetrated, three-dimensional (3D) self-penetrated, or one-dimensional (1D) polyrotaxane topological features. Isostructural {[M(tere)(bpfp)(H(2)O)(2)]?4H(2)O}(n) phases (1, Zn; 2, Co) exhibit mutually inclined 2D + 2D → 3D interpenetration of gridlike layers. {[Cd(4)(tere)(4)(bpfp)(3)(H(2)O)(2)]·8H(2)O}(n) (3) possesses a novel 3,4,8-connected trinodal self-penetrated network with (4.6(2))(2)(4(2)6(16)8(7)10(3))(4(2)6(4))(2) topology. [Zn(2)Cl(2)(tere)(bpfp)(2)](n) (4) is the first example of a 1D + 1D → 1D polyrotaxane coordination polymer, to the best of our knowledge. Metal coordination geometry plays a crucial role in dictating the overall dimensionality in this system. Thermal decomposition behavior and luminescent properties of the d(10) configuration metal derivatives are also presented herein.     

Hydrothermal syntheses, crystal structures, and characteristics of a series of Cd-btx coordination polymers (btx = 1,4-Bis(triazol-1-ylmethyl)benzene)

Four novel cadmium-btx (btx = 1,4-bis(triazol-1-ylmethyl)benzene) coordination polymers [Cd(btx)(2)(NO(3))(2)](n)(1), [Cd(btx)(2)Cl(2)](n)(2), [Cd(btx)(SO(4))(H(2)O)(2)](n)(3), and [Cd(btx)(S(2)O(7))(H(2)O)](n)(4) have been prepared by hydrothermal reaction (140 or 180 degrees C) 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 CdSO(4) 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 alpha(2) value of 1.15 x 10(-)(9) m 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.     

Novel one-dimensional polymers generated from p-Ferrocenylbenzoate: syntheses, structures, and magnetic properties

Treatment of p-ferrocenylbenzoate [p-HOOCH4C6Fc, Fc = (eta5-C5H5)Fe(eta5-C5H5)] with Mn(OAc)2 x 2H2O or Cd(OAc)2 x 2H2O afforded one-dimensional linear chain polymer [[Mn(OOCH4C6Fc)2(mu2-OH2)(H2O)2](H2O)]n (1), double-bridge polymer [Mn(mu2-OOCH4C6Fc)2(phen)]n (phen = phenanthroline) (2), and ladderlike framework [[Cd(mu2-OOCH4C6Fc)(eta2-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 -3.25 cm(-1) for 1 and 2, respectively) are larger than those of most of the reported di-Mn(II) complexes that contain mu2-aqua and mu2-carboxylato units and one-dimensional Mn(II) carboxylic polymers.     

Synthesis, structure, and large optical limiting effect of the first coordination polymeric cluster based on an {I@[AgI(inh)]6} hexagram block

In this paper, treatment of N-(isonicotinoyl)-N'-nicotinoylhydrazine (inh) and AgI with excess KI afforded a unique coordination polymeric cluster {[AgI(inh)]6(KI)}n (1) with the hexagram cluster units centered by mu6-I. In the polymer these hexagram units are parallel to the ab plane and are linked by separated K+ centers through inh. Polymer 1 represents the first example of coinstantaneous cation-anion-induced supramolecular self-assembly with nanoscale inner cavities. The polymer's third-order nonlinear optical (NLO) properties were determined by the Z-scan technique in DMF solution. The results show that the polymer has strong third-order optical nonlinearities. The nonlinear absorptive index a2 and refractive index n2 are calculated to be 1.044 x 10(-9) mW(-1) and 2.827 x 10(-11) esu, respectively. The values are comparable to those of the reported cluster polymers. The optical limiting experiments show that the present cluster exhibits a large optical limiting capacity. The value of the limiting threshold was measured as 0.53 J cm(-2) from the optical limiting experimental data. This value is three times better than 1.6 J cm(-2) of C60. This paper also gives a summary and comparison on the optical limiting properties of oligomeric and polymeric clusters.     

Reactions of a tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [Et(4)N][Tp*WS(3)] with CuX (X = Cl, NCS, or CN): isolation, structures, and third-order NLO properties

Reactions of a tungsten trisulfido complex of hydridotris(3,5-dimethylpyrazol-1-yl)borate (Tp*) [Et4N][Tp*WS3] (1) with 3 equiv of CuCl in CHCl3 afforded a tetranuclear anionic cluster [Et4N][Tp*W(mu3-S)3(CuCl)3] (2), while that of 1 with 3 equiv of CuNCS in MeCN produced a decanuclear neutral cluster (major product) [Tp*W(mu3-S)3Cu3(mu-NCS)3(CuMeCN)]2 (3) along with a binuclear anionic cluster (minor product) [Et4N][Tp*WO(mu-S)2(CuNCS)] (4). Solvothermal reactions of 1 with 3 equiv of CuCN in MeCN at 80 degrees C for 48 h followed by slowly cooling it to ambient temperature gave rise to a polymeric cluster [Tp*W(mu3-S)(mu-S)2Cu2(MeCN)(mu-CN)]n (5). Compounds 2-5 were characterized by elemental analysis, IR, UV-vis, 1H NMR, and single-crystal X-ray crystallography. The cluster anion of 2 has a [Tp*WS3Cu3] incomplete cube with one Cl atom coordinated at each Cu center. 3 is composed of an unprecedented centrosymmetric W2Cu8 cluster core in which each void of the two single incomplete cubane-like [Tp*W(mu3-S)3Cu3(mu-NCS)]+ cations is partially filled with an extra [Cu(MeCN)(mu-NCS)2]- anion via a pair of Cu-mu-NCS-Cu bridges. The cluster anion of 4 contains one WS2Cu core that is formed by an oxidized [Tp*WO(mu-S)2] species and one CuNCS fragment. 5 consists of butterfly shaped [Tp*W(mu3-S)(mu-S)2Cu2(MeCN)] fragments that are interconnected via cyanide bridges to form a 1D spiral chain extending along the c axis. The successful synthesis of 2-5 from 1 suggests that 1 may be an excellent synthon to the W/Cu/S clusters. In addition, the third-order nonlinear optical (NLO) properties of 1-3 in solution were also investigated by femtosecond degenerate four-wave mixing (DFWM) technique with a 80 fs pulse width at 800 nm. Although 2 was not detected to have NLO effects, 1 and 3 exhibited relatively good optical nonlinearities with the nonlinear refractive index n2 and the third-order nonlinear optical susceptibility chi(3) values being 0.79 x 10(-13) and 0.38 x 10(-14) esu (1) and 2.08 x 10(-13) and 1.00 x 10(-14) esu (3), respectively. The second-order hyperpolarizability gamma value for 3 (5.46 x 10(-32) esu) is ca. 5 times larger than that of its precursor 1.     

系列Co-aip聚物的合成、结构及表面光电性能

采用水热法合成了3种以5-氨基间苯二甲酸根为桥连配体的Co(Ⅱ)配聚物:[Co2(aip)2(bipy)]n·2nH2O(1),[Co(aip)(imH)]n(2)和[Co(aip)(phen)]n(3)(H2aip=5-氨基间苯二甲酸,bipy=2,2′-联吡啶,imH=咪唑,phen=1,10-邻菲啰啉).通过X射...     

Two Novel 3D Copper Phthalate Coordination Complexes Incorporating Isomeric Flexible Bis(pyridylformyl)piperazine Ligands

Two novel metal‐organic coordination complexes [Cu(3‐bpfp)(pht)(H₂O)] · 2H₂O ( 1 ) and [Cu₃(4‐bpfp)(pht)₂(OH)₂] · 2H₂O ( 2 ) were hydrothermally synthesized by self‐assembly of phthalic acid (H₂pht), flexible bis(pyridylformyl)piperazine ligands [3‐bpfp = bis(3‐pyridylformyl)piperazine, 4‐bpfp = bis(4‐pyridylformyl)piperazine], and copper chloride. Single crystal X‐ray diffraction analysis revealed that the adjacent Cu^II ions are connected by pht showing different coordination modes [a bis(monodentate) coordination mode for 1 and a monodentate‐bidentate coordination mode for 2 ] to form 1D Cu‐pht‐Cu chains in 1 and 2D Cu‐pht layers in 2 . In compound 1 , a twofold interpenetrated CdSO₄‐like topology is formed by connection of 3‐bpfp. Using the isomeric ligand 4‐bpfp instead of 3‐bpfp resulted in the formation of 2 , which displays a novel 3, 4, 4, 4‐connected tetranodal 3D coordination polymeric framework. The ligand 3‐bpfp adopts a μ₂‐bridging coordination mode in 1 (by ligation of the pyridyl nitrogen atoms), whereas the ligand 4‐bpfp adopts a μ₄‐bridging coordination mode (by ligation of pyridyl nitrogen and carbonyl oxygen atoms) in 2 . Moreover, the electrochemical properties of carbon paste electrodes bulk modified with the two copper complexes were studied.     

Metal‐ and Substituent‐Dependent Structural Diversity in ­Cobalt and Nickel Isophthalate Coordination Polymers with Bis(4‐pyridylformyl)piperazine Tethers

Hydrothermal reactions of nickel or cobalt nitrate with the dipyridylamide ligand bis(4‐pyridylformyl)piperazine (4‐bpfp) and either 5‐methoxyisophthalate (H₂omeip) or 5‐methylisophthalate (H₂mip) afforded a series of coordination polymers that were structurally characterized by single‐crystal X‐ray diffraction. Different synthetic conditions afforded the 1D chain phase {[Ni(Homeip)₂(H₂omeip)(bpfp)] · 2H₂O}_n ( 1 ) or the mutually inclined interpenetrated (4, 4) grid system in {[Ni(omeip)(bpfp)(H₂O)] · 2H₂O}_n ( 2 ). The analogous cobalt phase {[Co(omeip)(bpfp)] · 3H₂O}_n ( 3 ) lacks bound water molecules, which enforces a non‐interpenetrated (4, 4) grid structure based on {Co₂(OCO)₂} dinuclear clusters. Similar clusters are seen in {[Co(mip)(bpfp)(H₂O)₂] · 3.5H₂O}_n ( 4 ), which manifests a 1D ribbon structural motif. Its nickel congener {[Ni(Hmip)₂(bpfp)(H₂O)₂] · 2H₂mip}_n ( 5 ) also shows a 1D chain motif. A variable temperature magnetic susceptibility study indicates antiferromagnetic coupling within the dimeric units in 3 and 4 concomitant with single ion effects. Additionally, thermal degradation properties of these new materials are described.     

Hydrothermal synthesis, structure, and luminescent properties of selected Zn(II)/Cd(II) coordination polymers constructed from 3,5-bis(x-pyridyl)-1,2,4-triazole (x = 3, 4)

Utilizing 3,5-bis(x-pyridyl)-1,2,4-triazole (x-Hpytz, x = 3; x = 4) as multidentate ligands, six novel coordination polymers with Zn(II) or Cd(II) metal ions were prepared: [Zn(3-pytz)(0.5)(OH)(0.5)Cl](n) (1, 1D ladder), {[Zn(3-Hpytz)(H(2)O)(4)] [Zn(3-Hpytz)(H(2)O)(3)·SO(4)]SO(4)·5H(2)O}(n) (2·5H(2)O, 1D chain), [Cd(3-Hpytz)(SO(4))](n) (3, 3D framework), {[Cd(3-Hyptz)SO(4)·3H(2)O]·2H(2)O}(n) (4·2H(2)O, 1D chain), [Zn(4-pytz)Cl](n) (5, 3D framework) and [Zn(2)(4-pytz)(SO(4))(OH)](n) (6, 3D framework). All compounds were obtained from hydrothermal reactions, with the exception of compound 4 which was obtained by solvent diffusion at room temperature. All compounds were characterized by FTIR, elemental analysis and TGA analysis and their structures were determined by X-ray diffraction. All compounds exhibited substantial thermal stability and showed photofluorescent properties that resulted from ligand π-π* transition.     

D-π-A-π-D型双查尔酮衍生物的合成和三阶非线性光学性质

合成一种新颖的D-π-A-π-D型双查尔酮衍生物2,6-二[3-(4-甲氧基苯基)]丙烯酰基吡啶,经IR,~1H NMR和HR-MS对其结构进行表征,采用4f相位相干成像技术测定了它的三阶NLO性质并确定了相关参数:脉宽4ns,激光波长450nm,非线性吸收系数β=0.9×10~(-9) m/W,非线性折射率n_2=-0.42×10~(-16) m~2/W,三阶非线性极化率χ~((3))=4.10×10~(-19) m~2/V~2;并测定了紫外光谱和DSC曲线.     

One-dimensional azido-bridged chiral metal complexes with ferromagnetic or antiferromagnetic interactions: syntheses, structures, and magnetic studies

One-dimensional chiral copper(II) and manganese(II) coordination polymers with single asymmetric end-to-end (EE) azide bridges, [Cu(R-L)2(N3)]n(ClO4)n (1), [Cu(S-L)2 (N3)]n(ClO4)n (2), [Mn(R-L)2(N3)]n(ClO4)n (3), and [Mn(S-L)2(N3)]n(ClO4)n (4) (R-L or S-L = R- or S-pyridine-2-carbaldehyde-imine), have been synthesized, using azide ions as bridging groups and chiral Schiff bases as auxiliary ligands, and characterized. The crystal structure determination of complexes 1 and 2 reveals the formation of one-dimensional chiral chains, in which the central Cu(II) ion is six-coordinate in the form of an elongated octahedron. Complex 3 consists of chiral helical polymeric chains, in which the central Mn(II) has a slightly distorted octahedral geometry. They all crystallize in the chiral space group P2(1). Complexes 1 and 2 are rare examples that exhibit ferromagnetic interaction between copper(II) ions through the single end-to-end azido bridge. Fitting the susceptibility data for 1 using a 1D uniform chain model led to the parameters J = 0.70(3) cm(-1), g = 2.06(2), and zj' = 0.07(2) cm(-1). The magnetic studies on 3 and 4 show that there is weak antiferromagnetic coupling between the manganese(II) ions.     

Investigation on structures, luminescent and magnetic properties of Ln(III)-M (M = Fe(II)(HS), Co(II)) coordination polymers

The structures, luminescent and magnetic properties of three series of coordination polymers with formulas-{[Fe(3)Ln(2)(L(1))(6)(H(2)O)(6)]·xH(2)O}(n) (Ln = Pr-Er; 1-9), {[Co(3)Ln(2)(L(1))(6)(H(2)O)(6)]·yH(2)O}(n) (Ln = Pr-Dy, Yb; 10-17) and {[Co(2)Ln(L(2))(HL(2))(2)(H(2)O)(7)]·zH(2)O}(n) (Ln = Eu-Yb; 18-25) (H(2)L(1) = pyridine-2,6-dicarboxylic acid, H(3)L(2) = 4-hydroxyl-pyridine-2,6-dicarboxylic acid) were systematically explored in this contribution. [Fe(II)(HS)-L(1)-Ln(III)] (1-9) and [Co(II)-L(1)-Ln(III)] (10-17) series are isostructural, and display 3D porous networks with 1D nanosized channels constructed by Fe/Co-OCO-Ln linkages. Furthermore, two types of "water" pipes are observed in 1D channels. [Co(II)-L(2)-Ln(III)] (18-25) series exhibit 2D open frameworks based on double-stranded helical motifs, which are further assembled into 3D porous structures by intermolecular hydrogen bonds between hydroxyl groups. The variety of the resulting structures is mainly due to the HO-substitution effect. These 3D coordination polymers show considerably high thermal stability, and do not decomposed until 400 °C. The high-spin Fe(II) ion in [Fe(II)(HS)-L(1)-Ln(III)] was confirmed by X-ray photoelectron spectroscopy, M?ssbauer spectroscopy and magnetic studies. The luminescent spectra of coordination polymers associated with Sm(III), Eu(III), Tb(III) and Dy(III) were systematically investigated, and indicate that different d-metal ions in d-f systems may result in dissimilar luminescent properties. The magnetic properties of [Fe(II)(HS)-L(1)-Ln(III)] (3, 6, 7, 9, 13), [Co(II)-L(1)-Ln(III)] (15-17) and [Co(II)-L(2)-Ln(III)] (19-24) coordination polymers were also studied, and the χ(M)T values decrease with cooling. For the single ion behavior of Co(II) and Ln(III) ions, the magnetic coupling nature between Fe(II)(HS)/Co(II) and Ln(III) ions cannot be clearly depicted as antiferromagnetic coupling.     

Systematic investigation of the hydrothermal syntheses of Pr(III)-PDA (PDA = pyridine-2,6-dicarboxylate anion) metal-organic frameworks

A series of novel two-dimensional (2D) and three-dimensional (3D) praseodymium coordination polymers, namely, {[Pr3(PDA)4(HPDA)(H2O)8] x 8H2O}n (2), {[Pr2(PDA)3(H2O)3] x H2O}n (3), {[Pr(PDA)(H2O)4] x ClO4}n (4), and { [Pr2(PDA)2(H2O)5SO4] x 2H2O}n (5) (PDA = pyridine-2,6-dicarboxylic anion), was designed and synthesized under hydrothermal conditions. Complexes 1-3 (chainlike polymer, {[Pr(PDA)(HPDA)(H2O)2] x 4H2O}n (1) was also obtained independently by us, although it has been reported recently by Ghosh et al.) were fabricated successfully by simply tuning the Pr/PDA ratio and exhibited various and intriguing topological structures from a 1D chain to a 3D network. While the synthetic strategy of 5 was triggered and further performed only after 1 was structurally characterized. The complexes were characterized by X-ray single-crystal determination, spectroscopic, and variable-temperature magnetic susceptibility analyses. In complex 2 an unusual nanosized square motif as a building block constructed by eight Pr ions was further assembled into a highly ordered 2D grid compound. In complex 3 the decanuclear Pr metal-based structure as a repeat unit interpenetrated to form a novel 3D polymer. Complex 4 was a 3D network polymer fabricated through a hexanuclear Pr ring as a building block, and ClO4- anions as guests were trapped in the cavity. In complex 5 six Pr atoms, two SO4(2-) anions, and carboxylic oxygen bridges constructed an intriguing rectangle structure as a repeat unit in the grid to form a 2D coordination polymer in which the unique bi-bidentate coordination mode of SO4(2-) anion was observed.     

Synthesis of Poly[（3-octanoylpyrrole-2,5-diyl）-p-（N, N-dimethylamino）benzylidene] and Its Properties by Nitrogen Ion Implantation

Introduction Nonlinearoptical(NLO)organicpolymers havereceivedincreasingattentionbecauseoftheir excellentbehaviorandthegoodprospectsoftheir applicationsinhigh-techareas,suchasoptical communication,high-densityopticalstorageand all-opticalinformationprocess.Poly(pyrrolylme- thine)isanNLOmaterialwithpromisingapplica- tions[1_3].However,itssolubilityandfilm-forming performancearepoor.Inthispaper,anovelsolu- blepoly(pyrrolylmethine),poly[(3-octanoyl-pyr- role-2,5-diyl)-p-(N,N-dimethylamino)ben…     

Cobalt(II)-(dpyo)-dicarboxylate networks: unique H-bonded assembly and rare bridging mode of dpyo in one of them [dpyo = 4,4'-dipyridyl N,N'-dioxide

Polymeric networks, {[Co(dpyo)(ox)]}(n) (1), {[Co(dpyo)(fum)(H(2)O)(2)]}(n) (1) and {[Co(dpyo)(tp)(H(2)O)(2)] x [Co(H(2)O)(6)] x (tp) x (H(2)O)}(n) (3) [ox = oxalate dianion, fum = fumarate dianion, tp = terephthalate dianion and dpyo = 4,4'-dipyridyl N,N'-dioxide] have been synthesized and characterized by single crystal X-ray diffraction analyses. The structural determination reveals 1 and 2 are covalent bonded 2D networks of 4,4 topology and of these, complex 2 undergoes a H-bonding scheme resulting in a 3D supramolecular architecture. Complex 3 is a 1D coordination polymer built up by almost collinear hexacoordinated Co(ii), doubly bridged by a tp carboxylate group and a dpyo oxygen, which in combination with lattice [Co(H(2)O)(6)](2+), tp and water molecules shows an unprecedented 3D supramolecular network through H-bonding. In the polymer the dpyo shows novel mu-4,4 bridging mode towards the cobalt ion. Low temperature magnetic interaction reveals antiferromagnetic coupling in all of the complexes.     

1D helix, 2D brick-wall and herringbone, and 3D interpenetration d10 metal-organic framework structures assembled from pyridine-2,6-dicarboxylic acid N-oxide

Five novel interesting d(10) metal coordination polymers, [Zn(PDCO)(H2O)2]n (PDCO = pyridine-2,6-dicarboxylic acid N-oxide) (1), [Zn2(PDCO)2(4,4'-bpy)2(H2O)2.3H2O]n (bpy = bipyridine) (2), [Zn(PDCO)(bix)]n (bix = 1,4-bis(imidazol-1-ylmethyl)benzene) (3), [Zn(PDCO)(bbi).0.5H2O]n (bbi = 1,1'-(1,4-butanediyl)bis(imidazole)) (4), and [Cd(PDCO)(bix)(1.5).1.5H2O]n (5), have been synthesized under hydrothermal conditions and structurally characterized. Polymer 1 possesses a one-dimensional (1D) helical chainlike structure with 4(1) helices running along the c-axis with a pitch of 10.090 Angstroms. Polymer 2 has an infinite chiral two-dimensional (2D) brick-wall-like layer structure in the ac plane built from achiral components, while both 3 and 4 exhibit an infinite 2D herringbone architecture, respectively extended in the ac and ab plane. Polymer 5 features a most remarkable and unique three-dimensional (3D) porous framework with 2-fold interpenetration related by symmetry, which contains channels in the b and c directions, both distributed in a rectangular grid fashion. Compounds 1-5, with systematic variation in dimensionality from 1D to 2D to 3D, are the first examples of d(10) metal coordination polymers into which pyridinedicarboxylic acid N-oxide has been introduced. In addition, polymers 1, 4, and 5 display strong blue fluorescent emissions in the solid state. Polymer 3 exhibits a strong SHG response, estimated to be approximately 0.9 times that of urea.     

Syntheses,Crystal Structures,and Fluorescence Properties of Three Coordination Polymers Constructed Based on Benzoic Acid and Its Derivatives

Three new different dimensional coordination polymers, namely, [Zn(BA-)2(4,4?-bib)-1.5]n(1), [Zn(4-Br BA-)2(1,4-bmb)]n(2) and [Mn(4-Br BA)2(4,4?-bib)]n(3) have been assembled through the mixed-ligand synthetic strategy(4-HBr BA = 4-bromobenzoic acid, HBA = benzoic acid, 1,4-bmb = 1,4-bis(1 H-imidazol-4-yl)benzene, 4,4?-bib = 4,4?-bis(imidazolyl)biphenyl). Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses(EA), powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. Single-crystal X-ray diffraction analysis reveals that the crystals of complexes 1~3 are all in triclinic systems, space group P1. Complexes 1 and 2 are 0D binuclear structures, and 3 is a 1 D chain. Moreover, the solid state fluorescence properties of 1 and 2 have been investigated.