Zhaoxun Lian

Structures and third-order nonlinear optical properties of two three-dimensional Cd(II) coordination polymers with trinodal (3, 4, 5) and dinodal (4, 5) connected network topologies

Two Cd(II) coordination polymers, [Cd3(1,2-bib)4(STP)2(H2O)2]·10H2O (1) and [Cd3(1,3-bib)5(STP)2]·3H2O (2) (1,2-bib = 1,2-bis(imidazol-l-yl-methyl)benzene; 1,3-bib = 1,3-bis(imidazol-l-yl-methyl)benzene; NaH2STP = sodium 3,5-dicarboxybenzenesulfonate), have been synthesized under hydrothermal conditions. Compound 1 presents a 3-nodal (3, 4, 5)-connected 3D framework with a point (Schlafli) symbol (4·62)2(42·64·84)2(42·84). Compound 2 exhibits a 3D framework with 2-nodal (4, 5)-connected (42·53·65)2(52·64) topology. The third-order nonlinear optical (NLO) properties of two compounds were determined in DMSO solution and thin films by a Z-scan technique. They show strong third-order nonlinear optical (NLO) absorption with absorptive coefficients β(MKS) 6.53 × 10−11 m W−1 for 1 and 7.15 × 10−11 m W−1 for 2 in DMSO solution. The third-order NLO susceptibility χ(3) is calculated as 2.23 × 10−12 for 1, 2.50 × 10−12 esu for 2 in DMSO solution. While in thin films, both compounds show stronger NLO absorption with absorptive coefficients β(MKS) 31.1 × 10−6 m W−1 for 1 and 3.80 × 10−6 m W−1 for 2, and third-order NLO susceptibility χ(3) is calculated as 1.09 × 10−6 for 1, 0.13 × 10−6 esu for 2. The electronic structures of the two compounds were investigated by density functional theory (DFT). The composition of the frontier orbitals and the origin of the NLO properties of the two compounds were discussed.

Bis(μ-4-carboxy-2-sulfonatobenzoato)bis[aqua(2,2′-bipyridyl)manganese(II)]

In the title compound, [Mn(2)(C(8)H(4)O(7)S)(2)(C(10)H(8)N(2))(2)(H(2)O)(2)], pairs of hexacoordinated manganese(II) centres are bridged by 2-sulfonatoterephthalate(2-) anions to form cyclic centrosymmetric dimers, which are linked into sheets by O-H...O hydrogen bonds.

Synthesis, structures, and third-order nonlinear optical properties of three new copper complexes based on salicylaldehyde phenoxyacetohydrazide ligand

Three copper complexes, [Cu2(Hsa)2(pipe)]·2DMF (1), [Cu(Hsa)(MEA)]n (2), and {[Cu4(Hsa)4(DMF)](DMF)}n (3) (pipe = piperazine; MEA = methenamine, Hsa = (2-hydroxybenzylidene)-2-phenoxyacetohydrazide), have been synthesized in methanol/DMF solution at room temperature and structurally characterized by single-crystal X-ray diffraction. In 1, the copper(II) complexes are bridged by pipe ligands to form binuclear clusters. In 2, the MEA ligands link copper(II) complexes to result in an infinite chain structure. Compound 3 contains tetranuclear clusters, which are bridged by Hsa to give an infinite chain structure. Third-order nonlinear optical (NLO) properties of the compounds were determined by Z-scan technique in DMF solution. All three compounds show very strong NLO absorption properties with absorptive coefficients β(MKS), 1.71 × 10−10 m W−1 for 1, 1.39 × 10−10 m W−1 for 2, and 9.30 × 10−11 m W−1 for 3, respectively. The NLO refractive index value γ(MKS) of 3 is 5.97 × 10−18 m2 W−1. Compound 3 shows strong self-focusing behavior. Graphical Abstract Three copper complexes have been synthesized in methanol/DMF solution at room temperature. The compounds show very strong NLO absorption properties

Crystal structures and investigation of the third-order nonlinear optical properties of four coordination polymers by using the Z-scan technique

The present paper reports the structures and the third order nonlinear optical properties of four coordination polymers prepared by hydrothermal methods using nickel acetate or cobalt acetate, bisimidazolyl ligands and different aromatic carboxylic acids, namely [Co(H2O)2(1,2-BIB)2][Co(DBS)(1,2-BIB)]2·7H2O (1), [Ni(H2O)2(1,2-BIB)](CBA)·H2O (2), [Ni(1,2-BIB)(SDA)]·4H2O (3) and [Ni(H2O)(1,2-BIB)(HBTA)]·2H2O (4) (1,2-BIB = 1,2-bis((1H-imidazol-1-yl)methyl)benzene, H2DBS = sodium 3,5-dicarboxybenzenesulfonate, H2CBA = 2-(carboxymethyl)benzoic acid, H2SDA = 4,4′-sulfonyldibenzoic acid and H3BTA = benzene-1,3,5-tricarboxylic acid). Compound 1 has a one-dimensional structure, containing a polymeric cationic chain and a polymeric anionic chain. In compound 2, the Ni(II) ions are alternately linked by 1,2-BIB ligands and CBA ligands to form a joint-like chain structure. In compound 3, the metal ions are connected by 1,2-BIB to form a ladder-like structure, and SDA ligands are located on both sides of the chain. In compound 4, the Ni(II) ions are alternately connected by 1,2-BIB and BTA ligands to form a two-dimensional structure. We investigated the third-order nonlinearity of the compounds by a single-beam Z-scan technique. Interestingly, the compounds exhibit different third-order nonlinearities. Compound 1 has a saturable absorption (SA) and a self-defocusing effect with the nonlinear absorption coefficient β being −12.4 × 10−7 m W−1 and the nonlinear refractive index γ being −8.51 × 10−14 m2 W−1. Compound 2 presents only a self-defocusing effect with the nonlinear refractive index γ being −128.87 × 10−14 m2 W−1, while compounds 3 and 4 show a reverse-saturation absorption (RSA) effect with the nonlinear absorption coefficient β being 4.42 × 10−7 and 2.97 × 10−7 m W−1, respectively. We calculated the band structure and the total (TDOS) and partial density of states (PDOS) of the four compounds. The calculated results are satisfactory for explaining the experimental results. This shows that intramolecular MLCTs or LMCTs have a significant impact on the third-order nonlinearity of the compounds.

Crystal structures and third-order optical properties of three manganese(II) complexes constructed from N-heterocyclic and polycarboxylate ligands

Abstract Three new manganese(II) complexes, {[Mn(PTP)]2[Mn(PTP)(H2O)]}(BTA)2·2H2O (1), [Mn(PTP)(ODA)]2 (2), and [Mn(FTP)(ODA)]2·H2O (3), were synthesized by the reactions of manganese acetate and polycarboxylic acid in the presence of N-heterocyclic ligands (where PTP=4′-phenyl-2,2′:6′,2″-terpyridine, H3BTA=benzene-1,3,5-tricarboxylic acid, H2ODA=4,4′-oxydibenzoic acid, FTP=4′-(furan-2-yl)-2,2′:6′,2″-terpyridine). In complex 1, each BTA ligand serves as a μ3-bridge to link three Mn(II) centers, whereas each Mn(II) center is coordinated by two BTA ligands. This connection mode results in a grid sheet. Complexes 2 and 3 have very similar molecular structures with Mn(II) centers connected by ODA ligands to result in ring-like arrays. We investigated the third-order nonlinear optical (NLO) properties of the three complexes by single beam Z-scan techniques. Complexes 1–3 exhibit strong third-order NLO reverse saturable absorption with NLO absorptive indices β=1.32×10−6, 3.01×10−6, and 9.42×10−6 m W−1, respectively. In addition, complex 1 shows all excellent self-focusing effect with an NLO refractive index of γ=1.25×10−12 m2 W−1. The third-order NLO susceptibility χ(3) of the three complexes were calculated as 47.55×10−8, 4.85×10−8, and 15.16×10−8 esu, respectively.

Crystal structure of poly-[(μ6-benzene-1,2,4,5-tetracarboxylato)-(μ2-1,2-bis(imidazol-1-ylmethyl)benzene)dicobalt(II)], Co2C24H16N4O8

Abstract Co2C24H16N4O8, triclinic, P1̅ (no. 2), a = 7.3859(13) Å, b = 9.5719(17) Å, c = 16.442(3) Å, α = 77.450(3)°, β = 85.065(3)°, γ = 84.844(3)°, V = 1127.4(3) Å3, Z = 2, Rgt(F) = 0.0457, wRref(F2) = 0.1058, T = 296(2) K.

Crystal structure of catena-(bis(μ2-1, 2-bis(imidazole-1-ylmethyl)benzene-κN:N′)-dichlororido-nickel(II)), C28H28Cl2N8Ni

Abstract C28H28Cl2N8Ni, monoclinic, P21/c, a = 8.521(5) Å, b = 10.255(6)) Å, c = 15.414(9) Å, β = 91.209(9)°, V = 1346.6(13) Å3, Z = 2, Rgt(F) = 0.0360, wRref(F2) = 0.0916, T = 296(2) K.

Crystal structure of catena-(bis(μ2-5-nitro-1,3-benzenedicarboxlato)- hexakis(imidazole)dimanganese(II) dihyrate, Mn2(C3H4N2)6(C8H3NO6)2 · 2H2O

C34H34Mn2Ni4Oi4, orthorhombic, Pnah (no. 33), a = 13.459(3) Â, b = 16.442(4) Â, c = 18.273(4) Â, V = 4043.7 Â, Ζ = 4, RgJF) = 0.053, wRKf(F) = 0.132, T 298 K.

catena-Poly[[(2,2′-bipyridyl)oxidovanadium]-di-μ2-oxido-[(2,2′-bipyridyl)oxidovanadium]-μ3-selenito-bis[(2,2′-bipyridyl)dioxidovanadium]-μ3-selenito]

: In the title compound, [V(4)O(8)(SeO(3))(2)(C(10)H(8)N(2))(4)], there are two distinct vanadium coordination environments. Alternating corner-shared VO(4)N(2) octahedra and SeO(3) pyramids result in eight-membered centrosymmetric V(2)Se(2)O(4) rings. In addition, pairs of V centres form centrosymmetric V(2)O(6)N(4) clusters via edge-sharing. These two kinds of secondary building units are linked in an ABABAB fashion to give an infinite chain whose nature is unprecedented in Se-V-O systems.