Dun-Ru Zhu

Application of ionic liquids containing tricyanomethanide [C(CN)3]- or tetracyanoborate [B(CN)4]- anions in dye-sensitized solar cells.

A series of novel ionic liquids composed of imidazolium, pyridinium, pyrrolidinium, and ammonium cations with tricyanomethanide or tetracyanoborate anions were prepared. The ionic liquids were characterized by NMR and IR spectroscopy and ESI-mass spectrometry, and their physical properties were investigated. Solid state structures of the N-propyl-N-methylpyrrolidinium and triethylpropylammonium tetracyanoborate salts were obtained by single crystal X-ray diffraction. The salts that are liquid at room temperature were evaluated as electrolyte additives in dye-sensitized solar cells, giving rise to efficiencies 7.35 and 7.85% under 100 and 10% Sun, respectively, in combination with the standard Z907 dye.

Magnetic properties of two 1D complexes with mixed bridging ligands

The crystal structure of a 1D chain complex, [Cu(SCN)(deae)]n (1) (Hdeae N,N-diethylamino ethanol), with mixed bridges was determined. The structure is composed of a dimeric Cu(II) unit with two bridging m 3 -h 2 -aminoethanolato ligands, while the units are bridged by end-to-end thiocyanato groups to form a 1D chain. The variable temperature magnetic susceptibility of 1 and [Cu(SCN)(dmae)]n (2) (HdmaeN,N-dimethylamino ethanol) in the temperature 5‐300 K have been interpreted in terms of simple dimer model approximation (H 2JSA·SB). The magnetic behaviors show that the aminoethanolato bridges mediate a moderately strong antiferromagnetic exchange interaction with the fitting values g 1.96(3), J 175(3) cm 1 for 1 and g2.016(7), J 205.4(7) cm 1 for 2, respectively.

Four MOFs with 2,2′-dimethoxy-4,4′-biphenyldicarboxylic acid: syntheses, structures, topologies and properties

Four novel metal–organic frameworks, [MnL(DMF)]n (1), [NiL(H2O)2(DMF)]n (2), [Cu2L2(H2O)2]·6H2O·2DMF (3), and Na2(Me2NH2)4[Cd7L10]·9H2O·17Me2NH·2DMF (4), were successfully synthesized in solvothermal conditions using 2,2′-dimethoxy-4,4′-biphenyldicarboxylic acid (H2L) as the ligand. The X-ray crystallography analysis reveals that MOF 1 exhibits a 3D framework with sra topology, while MOF 2 shows a 2D network with sql topology though they possess a similar secondary building unit (SBU) [MO6] (M = Mn for 1 and Ni for 2). MOF 3 reveals an unprecedented 4-fold interpenetrated 3D framework with lvt topology constructed from only planar 4-connected nodes ([Cu2(CO2)4] SBUs) with the rigid dicarboxylic acids. MOF 4 features an unique acentric 3D/3D hetero-interpenetrated framework built from two different nodes (4- and 8-connected), different chemical compositions [Cd(CO2)4 and Cd3(CO2)8], and different topology of networks (66 and 424·64) and contains an inorganic 1D chain consisting of a Na+ and three Cd2+ ions. The solid state 113Cd NMR spectrum indicates that 4 has three 6-, 7-, and 8-coordinated Cd2+ ions with chemical shifts at δ −25.3, −41.2 and −83 ppm, respectively. MOF 3 has two kinds of 1D channels with diameters of 11 A and 7 A and exhibits a selective gas adsorption for CO2–N2 and CH4–N2. MOF 4 shows a selective adsorption for cationic dyes and a nonlinear SHG activity (ca. 0.8 times that of urea).

A novel 2-D coordination polymer constructed from high-nuclearity waist drum-like pure Ho48 clusters

A novel 2-D coordination polymer constructed from high nuclearity nanosized Ho48 clusters was synthesised and structurally characterized using single-crystal X-ray analysis. The Ho48 cluster core with a charming waist drum-like structure was templated by CO3(2-) ions, and bridged by Ho-N bonds to get a 2-D coordination polymer.

An unprecedented 3D/3D hetero-interpenetrated MOF built from two different nodes, chemical composition, and topology of networks

An exceptional acentric MOF material with two-fold hetero-interpenetrated nets consisting of a 3D diamond network (mononuclear Cd(CO2)4 node) and a 3D CsCl framework (trinuclear Cd3(CO2)8 node) has been constructed, which contains 6-, 7-, 8-coordinated Cd2+ ions and shows a high thermal stability (>420 °C) and SHG activity.

Crystal and molecular structure of a novel complex [Mn(MOBPT)(H 2 O) 2 (NCS) 2 ] (MOBPT=4-( p -methoxyphenyl)-3,5-bis(pyridin-2-yl)-1,2,4-triazole)

The molecular structure of a novel manganese(II) complex with 4-(p-methoxyphenyl)-3,5-bis(pyridin-2-yl)-1,2,4-triazole (MOBPT) has been determined by X-ray analysis, FT-IR and by ESI-MS spectroscopy. The manganese atom is in a distorted octahedral environment. Bidentate chelating ligand (MOBPT) and two cis-oriented thiocyanate anions coordinate to the metal center equatorially and two water molecules coordinate axially. MOBPT entity coordinates via one triazole nitrogen and one pyridine nitrogen atom. The molecules are stabilized by intermolecular hydrogen bonds in the crystal lattice. Magnetic measurements show that the complex is high-spin species in the 75‐300 K range. q 2001 Elsevier Science B.V. All rights reserved.

Novel 3D lanthanide-organic frameworks with an unusual infinite nanosized ribbon [Ln3(μ3–OH)2(–CO2)6]+n (Ln = Eu, Gd, Dy): syntheses, structures, luminescence, and magnetic properties

Three novel lanthanide-organic frameworks, [Ln3(μ3–OH)2L2(HCO2)3(H2O)2]·H2O (Ln = Eu (1), Gd (2), Dy (3); H2L = 3,3′-dimethoxy-4,4′-biphenyldicarboxylic acid), have been prepared by the solvothermal reaction of Ln(NO3)3·6H2O and H2L in DMF/H2O mixed solvent. Crystallographic data show that 1–3 are isomorphous and crystallize in the monoclinic space groupP21/c. Each complex contains a rare infinite nanosized ribbon [Ln3(μ3–OH)2(–CO2)6]+n with three crystallographically distinct Ln(III) ions: two nine-coordinated and one eight-coordinated. The nanosized ribbons are interconnected through HCO2− anions and L2− linkers to yield a 3D framework. Furthermore, 1 exhibits strong red luminescence upon 343 nm excitation. The investigation of the magnetic properties shows the weak antiferromagnetic coupling between Gd(III) ions in 2 but ferromagnetic coupling between the Dy(III) ions in 3.

l- and d-[Ln(HCO2)(SO4)(H2O)]n (Ln = La, Ce, Pr, Nd, and Eu): Chiral Enantiomerically 3D Architectures Constructed by Double −[Ln–O]n– Helices

A total of 10 three-dimensional chiral coordination compounds L- and D-[Ln(HCO(2))(SO(4))(H(2)O)](n) (Ln = La, Ce, Pr, Nd, and Eu) have been synthesized without any chiral auxiliary and characterized by IR, thermogravimetric, and elemental analyses. Their structures were determined by single-crystal X-ray structural analysis, which shows that L-[Ln(HCO(2))(SO(4))(H(2)O)](n) (Ln = La, Ce, Pr, Nd, and Eu) crystallize in space group P4(3) and are laevogyrate and isostructural. The chiral frameworks of L-[Ln(HCO(2))(SO(4))(H(2)O)](n) are constructed from L-helical Ln-O cluster chains, while adjacent L-type helical -[Ln-O](n)- chains are connected through O-Ln-O linkages to form chiral intertwined Ln-O double helices of left-handedness. D-[Ln(HCO(2))(SO(4))(H(2)O)](n) crystallize in space group P4(1), and their chiral frameworks consist of D-helical Ln-O cluster chains. The observed second-harmonic-generation efficiencies of [La(HCO(2))(SO(4))(H(2)O)](n), Ce(HCO(2))(SO(4))(H(2)O)](n), [Pr(HCO(2))(SO(4))(H(2)O)](n), [Nd(HCO(2))(SO(4))(H(2)O)](n), and [Eu(HCO(2))(SO(4))(H(2)O)](n) are 0.7, 0.8, 0.7, 0.5, and 0.7 times that of urea, respectively. It is particularly interesting that [Pr(HCO(2))(SO(4))(H(2)O)](n) shows good two-photon absorption.

Two 3D metal–organic frameworks with different topologies, thermal stabilities and magnetic properties

Two novel 3D metal–organic frameworks, [ML]n (M = Co, 1; Mn, 2) were successfully prepared in solvothermal conditions using 3,3′-dimethoxy-4,4′-biphenyldicarboxylic acid (H2L) as the ligand. X-Ray crystallography analysis reveals that MOF 1 crystallizes in the monoclinic system, space group P21/c in contrast to MOF 2 in the tetragonal system, space group I. MOF 1 contains an elongated [CoO6] octahedron with two bound methoxy groups in the trans position, whereas MOF 2 has a compressed [MnO6] octahedron with two coordinated methoxy groups in the cis arrangement. The ligand L shows a novel bis(tridentate) bridging coordination mode. MOF 1 exhibits a 3D framework with CdSO4 (cds) topology consisting of two different nodes and good thermal stability (313 °C). MOF 2 is a doubly interpenetrated 3D α-Po framework with a higher thermal stability (368 °C). The study of magnetic properties in the temperature range of 1.8–300 K shows the occurrence of weak ferromagnetic interactions (J = 0.15 K) between the high-spin Co(II) ions in 1, but a weak antiferromagnetic coupling (J = −0.15 cm−1) between Mn(II) ions in 2 due to the syn-anti carboxylate bridge.

An Internal Fluorescent Probe Based on Anthracene to Evaluate Cation–Anion Interactions in Imidazolium Salts

A series of fluorescent imidazolium-based salts containing the cation [AnCH(2)MeIm](+) (in which An = anthracene and Im = the imidazolium cation) with Cl(-), BF(4)(-), PF(6)(-), SO(3)CF(3)(-), [N(CN)(2)](-), [N(SO(2)CF(3))(2)](-), or PhBF(3)(-) anions have been prepared and characterized. X-ray diffraction analysis of four of the salts reveals a number of C-H...X-type (X = O, N, F) hydrogen bonds between the hydrogen atoms from the imidazolium ring and in some cases from the anthracene ring with the electronegative atoms of the anions. Additionally, C-H...pi interactions can be found in all the salts analyzed by X-ray diffraction, whereas pi-pi stacking is observed only in the salt containing the phenyltrifluoroborate anion. Fluorescence emission analysis in acetonitrile shows that the fluorescence of these salts varies significantly according to the nature of the anion, and correlates to the extent of ion pairing present in solution. Photodimerization of these salts was observed, and in one case a dimer has been isolated and characterized by X-ray crystallography.