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1.
Abstract Two new 3-D supramolecular compouds: [Cu2X2(Hpyba)2]n (X = Br (1), I (2), Hpyba = 4-pyridin-4-yl-benzoic acid) have been hydrothermally synthesized and structurally characterized. Although both
compounds exhibit different space groups, they have a similar structure. Each {Cu2X2} cluster unit interconnects to form a 1D stair-step chain. The Saturated Hpyba ligands are regularly appended to both sides
of main chain, linked via N atoms of ligands. These infinite chains are further linked by H-bonds and π–π interactions to
form a 3-D supramolecular network structure. The thermal stability of 1 and 2 was investigated by thermogravimetric measurements.
Graphical Abstract Two new 3-D supramolecular compouds [Cu2X2(Hpyba)2]n (X = Br(1), I(2), Hpyba = 4-pyridin-4-yl-benzoic acid) have been obtained under hydrothermal conditions. Both compounds exhibit a 1D stair-step
chain structure based on the {Cu2X2} cluster units. These infinite chains are further linked by H-bonds and π–π interactions into forming a 3-D supramolecular
network with two types of channels along different directions.
相似文献
2.
Chun-Sen Liu E. Carolina Sañudo Li-Fen Yan Ze Chang Jun-Jie Wang Tong-Liang Hu 《Transition Metal Chemistry》2009,34(1):51-60
Abstract To explore the influence of the anthracene ring skeleton, with a large conjugated π-system, on the structures and properties
of its complexes, two MnII complexes with anthracene-9-carboxylate ligand were synthesized and structurally characterized: {[Mn(L)2(H2O)2](H2O)}∞ (1) and [Mn2(L)4(phen)2(μ-H2O)](CH3OH) (2) (L = anthracene-9-carboxylate and phen = 1,10-phenanthroline). Complex (1) has a one-dimensional (1D) chain structure that is further assembled to form a two-dimensional (2D) sheet, and then an overall
three-dimensional (3D) network by π···π stacking and/or C–H···π interactions. Complex (2) makes a dinuclear structure by incorporating the chelating phen ligand, which is further interlinked via inter-molecular
π···π stacking and C–H···π interactions to generate a higher-dimensional supramolecular network along the different crystallographic
directions. The results reveal that the bulky anthracene ring skeleton in L, by virtue of intra- and/or inter-molecular π···π
stacking and C–H···π interactions, plays an important role in the formation of complexes (1) and (2). The magnetic properties of (1) and (2) were further investigated. As expected, the very long inter-metallic separations result in weak magnetic coupling, with
the corresponding coupling constant values of J = −10 cm−1 for (1) and J = −2.46 cm−1 for (2).
Graphical abstract The constructions of two new MnII complexes comprising 1D chain (1) and dinuclear subunit (2) structures have been successfully achieved by using a bulky anthracene-9-carboxylic acid (HL), together with incorporating
the chelating 1,10-phenanthroline as a co-ligand for (2). The result reveals that the bulky anthracene ring skeleton of HL, by virtue of intra- and/or inter-molecular π···π stacking
and C–H···π interactions, plays an important role in the formation of the supramolecular architectures of (1) and (2). Moreover, magnetic properties of the complexes have been investigated.
相似文献
3.
Xiao-Bo Chen Hao-Hong Li Zhi-Rong Chen Ji-Bo Liu Jun-Bo Li Hai-Jun Dong Yan-Ling Wu 《Journal of Cluster Science》2009,20(3):611-620
Abstract A new hybrid coordination polymer {[Cu(II)(2,2′-bipy)3][Pb2I6]}
n
(1) was synthesized by the reaction of Cu(NO3)2, 2,2′-bipy, PbI2 and NaI in DMF/DMSO mixed solvent. As revealed by X-ray structural analysis, 1 consists of [Pb2I6]
n
2n− polyanions and discrete [Cu(II)(2,2′-bipy)3]2+ structure-directing agent cations. The polymeric negative chain [Pb2I6]
n
2− is built up by face-sharing of PbI6 octahedra. Structure-directing reagent cations and polymeric negative chains are in combination with each other by static
attracting force to form so-called hybrid structure. Experimental and theoretical optical property investigations indicate
that 1 possesses semiconductor property. DFT calculation was executed to probe the electronic structure of 1. To our interest, when using both second metal and π system as electronic tuning species, conjugated system is more preferable.
Graphical Abstract A new hybrid coordination polymer introduced transition-metal complex together with conjugated ligand was synthesized. Interestingly,
when using both second metal and π system as electronic tuning species, conjugated system is more preferable.
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4.
Nanthawat Wannarit Viwat Hahnvajanawong Chaveng Pakawatchai Sujittra Youngme 《Transition Metal Chemistry》2012,37(1):79-84
Two multiple-layer heterometallic MnII–AgI coordination polymers, {MnII(ampyz)(H2O)[Ag2I(CN)3][AgI(CN)2]·ampyz}
n
(1) and {[MnII(benzim)2[AgI(CN)2]2][(benzim)AgI(CN)]·H2O}
n
(2) where ampyz = 2-aminopyrazine and benzim = benzimidazole, have been prepared and structurally characterized. Compound 1 reveals a multiple-layer two-dimensional network with strong hexanuclear argentophilic interactions leading to an infinite
three-dimensional framework. Compound 2 has an unprecedented double-layer two-dimensional squared grid-type network with (4,4) topology through AgI···AgI and π–π interactions between two adjacent squared layers. These double-layer networks of 2 are linked to others by π–π interactions, leading to a three-dimensional framework. 相似文献
5.
Ming-Li Liu Jian-Min Dou Da-Cheng Li Da-Qi Wang Jian-Zhong Cui 《Transition Metal Chemistry》2012,37(1):117-124
The thiosemicarbazide and hydrazide Cu(II) complexes, [Cu3L21(py)4Cl2] (1), [Cu(HL2)py] (2) and [Cu(HL3)py] (3), (H2L1 = 1-picolinoylthiosemicarbazide, H3L2 = N′-(2-hydroxybenzylidene)-3-hydroxy-2-naphthohydrazide, H3L3 = 2-hydroxy-N′-((2-hydroxy-naphthalen-1-yl)methylene)benzohydrazide) have been prepared and characterized through physicochemical and spectroscopic
methods as well as X-ray crystallography. Complex 1 has a centrosymmetric structure with –N–N– bridged Cu3 skeleton. Neighboring molecules are linked into a 3D supermolecular framework by π–π stacking interactions, N–H···Cl and
C–H···Cl hydrogen bonds. Complexes 2 and 3 have similar planar structures but different dimers formed by concomitant Cu···N and Cu···O interactions, respectively. Solvent
accessible voids with a volume of 391 ?3 are included in the structure of complex 2, indicating that this complex is a potential host candidate. Thermogravimetric analysis shows that the three complexes are
stable up to 100 °C. 相似文献
6.
Abstract Two new Keggin-polyoxometalate hybrids, {[Cu2(4,4′-bpy)2][PW10VIW2VO40]}[Cu2(obpy)2]4 · 2 H2O (1) and {[Cu4(2,2′-bpy)4(4,4′-bpy)3][SiW12O40]} · 2H2O (2) (4,4′-/2,2′-bpy = 4,4′-/2,2′-bipyridyl, Hobpy = 6-hydroxy-2,2′-bipyridyl), were hydrothermally synthesized and structurally
characterized. Gillard type hydration of 2,2′-bipy is observed during the synthesis of 1, resulting in a new obpy ligand in situ. X-ray structural analyses show that 1 consists of 1D hybrid chain {[Cu2(4,4′-bpy)2][PW10VIW2VO40]}∞ and [Cu2(obpy)2] dimer, whereas 2 possesses 1D hybrid structure based on Keggin-type [SiW12O40]4− anions and tetra-nuclear copper complexes [Cu4(2,2′-bpy)4(4,4′-bpy)3]4+. Both compounds present interesting supramolecular architectures based on π–π stacking and hydrogen bonds.
Graphical Abstract Compounds {[Cu2(4,4′-bpy)2][PW12O40]}[Cu2(obpy)2]4 · 2H2O (1) and [Cu4(2,2′-bpy)4(4,4′-bpy)3][SiW12O40] · 2H2O (2) were hydrothermally synthesized. 1 features that the [Cu2(obpy)2] dimers based on in situ generated obpy ligands are stumped between the layers where 1D hybrid chain {[Cu2(4,4′-bpy)2][PW12O40]}∞ locates, while 2 exhibits 1D chain-like structure based on anions [SiW12O40]4− and tetra-copper complexes [Cu4(2,2′-bpy)4(4,4′-bpy)3]4+.
相似文献
7.
Ahmed A. Mohamed Hanan E. Abdou Andrew Mayer John P. Fackler Jr. 《Journal of Cluster Science》2008,19(4):551-559
Abstract Attempts to remove the halide atoms from [Au2(hpp)2Cl2], 1, Hhpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, with Ag(I) benzoate lead to the formation of the Au(I)–Ag(I) product, [(PhCOO)2Au4(hpp)4Ag2(PhCOO)4], 2. This material is stable to air and light at room temperature and shows a UV–vis spectrum in THF with absorbances at 575,
440, 345, and 273 nm. The mixed metal product crystallizes as green crystals in the monoclinic space group P21/n. The Au–Au distances of 2.4473(19) ? are the shortest gold–gold distances reported to date. The gold···silver distance is
3.344(3) ? and the silver···silver distance is 2.771(6) ?. This latter distance is short compared with the Ag···Ag distance
of 2.902(3) ? in the eight-membered silver benzoate dimer starting material. The Au(II) hpp and Ag(I) benzoate components
are linked by carboxylate groups and two gold-silver interactions. This result stands in structural contrast to terminal carboxylate
products observed with Au(II) ylides and amidinates wherein the carboxylate is not bridging to another metal atom.
Index Abstract Three equivalents of silver benzoate react with [Au2(hpp)2Cl2], 1, Hhpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine, to form the gold(II)-silver(I) product, 2, [(PhCOO)2Au4(hpp)4Ag2(PhCOO)4]. The gold–gold distance of 2.4473(19) ? is the shortest gold–gold distance reported to date. The gold–silver distance is
3.344(3) ? and the silver–silver distance is 2.771(6) ?.
Dedicated to the memory of F. Albert Cotton (1930–2007). 相似文献
8.
Two new CuI coordination polymers, [CuI(TATP) (CN)]
n
(1) and [CuI(bpy)(SCN)]
n
(2) (TATP = 1,4,8,9-tetranitrogen-trisphene, bpy = 2,2′-bipyiridine), have been synthesized under hydrothermal conditions and
structurally characterized by elemental analysis, IR, and X-ray crystallography. In 1 and 2, the metal centers are linked by bridging CN−/SCN− to form one-dimensional chains in the crystals and are stabilized by interchain π–π stacking interaction. 相似文献
9.
Hao-Hong Li Zhi-Rong Chen Yuan Liu Kai-Ning Ding Jun-Qian Li Chang-Cang Huang Liang-Qia Guo 《Journal of Cluster Science》2007,18(4):817-829
Two new organically templated copper halides, (nbq)4Cu4I8 (1) and [(ipq)2(Cu5I7)]
n
(2) have been synthesized in the presence of nbq+ and ibq+ (nbq+ = N-(n-butyl)-quinolinium, ibq+ = N-(iso-pentyl)-quinolinium) acting as structure-directing agents(SDAs). Both of the compounds present hybrid structures
with SDAs and inorganic moieties being incorporated. In 1, tetrameric Cu4I8
4− anion is composed by edge-sharing CuI4 tetrahedrons and CuI3 planar triangles. But the inorganic framework of 2 presents one-dimensional arrangement which results from the tetrahedron CuI4 and pseudo trigonal pyramid CuI3 through edge-sharing fashion. Electrostatic interactions between organic counter cations and inorganic moieties could be
observed and contribute to the crystal packing. Both compounds are further characterized by IR, UV–Vis, elemental analysis,
fluorescence and cyclic voltammetry. 相似文献
10.
Tarlok S. Lobana Parminderjit Kaur Alfonso Castineiras Peter Turner Timothy W. Failes 《Structural chemistry》2008,19(5):727-733
Abstract Monoclinic crystals of [Cu2(μ-I)2(PPh3)2(μ-N, S-pymSH)] · CH3CN) (1), were obtained by equimolar reaction of copper(I) iodide with pyrimidine-2-thione (pymSH), followed by the addition of triphenylphosphine
(PPh3) in acetonitrile. Crystal data for 1: space group P21, Z = 2, a = 9.896, b = 18.378, c = 11.703 ?, β = 101.73°. It has an iodo-bridged Cu(μ-I)2Cu core and the pyrimdine-2-thione binds to both Cu centers via N, S-bridging across the Cu(μ-I)2Cu core. This N, S-bridging, a rare coordination mode for pyrimidine-2-thione, leads to a short Cu···Cu separation of 2.675(2) ?
(sum of van der Waals radius of Cu atoms, 2.80 ?). The geometry around each Cu center is distorted tetrahedral with angles
varying in the range, ca. 102–119°. Copper(I) chloride and bromide also yielded monoclinic crystals of S-bonded tetrahedral monomers, [CuBr(pymSH)(PPh3)2] 2 and [CuCl(pymSH)(PPh3)2] 3. Crystal data for 2: space group P21/n, Z = 8, a = 12.825, b = 43.122, c = 13.396 ?, β = 90.79°. Crystal data for 3: space group P21/c, Z = 4, a = 14.340, b = 10.111, c = 24.200 ?, β = 94.36°. Compound 2 has two crystallographically independent molecules in crystal lattice. The 31P NMR spectrum of 1 showed two signals for PPh3 ligands bonded to two Cu centers with different coordination cores: CuI2PN and CuI2PS. Both 2 and 3 showed one signal each for PPh3 in their 31P NMR spectra.
Graphical abstract Reaction of copper(I) iodide with pyrimidine-2-thione and triphenylphosphine formed monoclinic crystals of dimer 1 with unusual N, S-bridging across Cu(μ2-I)2Cu core. 相似文献
11.
Smita Satapathi Subhasis Roy Kishalay Bhar Rajarshi Ghosh A. Srinivasa Rao Barindra K. Ghosh 《Structural chemistry》2011,22(3):605-613
Two binuclear cadmium(II) iodide compounds of the types [Cd2(L1)(I)4] (1) and [(L2)Cd(μ-I)CdI3] (2) [L1 = N,N′-(bis(pyridine-2-yl)formylidene)triethylenetetramine and L2 = tris(2-aminoethyl)amine] are synthesized and characterized.
X-ray structural study shows that each cadmium(II) in 1 has a distorted square pyramidal geometry with a CdN3I2 chromophore and that L1 behaves as a binucleating bis(tridentate) ligand bridging the metal centers with iodides remaining
as terminals. In 2, one cadmium(II) adopts a distorted tetrahedral geometry with a CdI4 chromophore surrounded by four iodides, while the other has a distorted trigonal bipyramidal environment with CdN4I chromophore bound by four N atoms of L2 and one bridging iodide. Weak C–H···π interactions in 1 result in an infinite 1D chain; however, such weak non-covalent interactions are absent in 2. The Schiff base complex, 1, shows high-energy intraligand 1(π–π*) fluorescence in DMF solution at room temperature, whereas compound 2 containing tripodal amine is fluorescent-inactive. 相似文献
12.
Abstract Two novel organic–inorganic composite phosphotungstates, [H9{Ce(α-PW11O39)2}Cu(en)2] · 6H2O (1) and H7[Cu(en)2{Er(α-PW11O39)2}Cu(en)2] · 12H2O (2) (en = ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW9O34]9− with CeIII or ErIII ions in the presence of Cu2+ ions and en, and structurally characterized by IR spectra, elemental analysis and thermogravimetric analysis. X-ray crystallographic
analyses indicate that they are all built by sandwich-type [Ln(α-PW11O39)2]11− (Ln = CeIII, ErIII) polyoxoanions and [Cu(en)2]2+ cations generating infinite one-dimensional arrangements. To our knowledge, this 1-D chain structures constituted by mono-Ln
sandwiched POM units and transition-metal complex cations are very rare.
Graphical Abstract Two novel organic–inorganic composite phosphotungstates, [H9{Ce(α-PW11O39)2}Cu(en)2] · 6H2O (1) and H7[Cu(en)2{Er(α-PW11O39)2}Cu(en)2] · 12H2O (2) (en = ethylenediamine) have been synthesized by the hydrothermal reaction of the trivacant Keggin polyoxoanion [α-A-PW9O34]9− with CeIII or ErIII ions in the presence of Cu2+ ions and en, and structurally characterized by IR spectra, elemental analysis and thermogravimetric analysis. X-ray crystallographic
analyses indicate that they are all built by sandwich-type [Ln(α-PW11O39)2]11− (Ln = CeIII, ErIII) polyoxoanions and [Cu(en)2]2+ cations generating infinite one-dimensional arrangements. To our knowledge, this 1-D chain structures constituted by mono-Ln
sandwiched POM units and transition-metal complex cations are very rare.
相似文献
13.
Franz A. Mautner Febee R. Louka August A. Gallo Jörg H. Albering Mohamed R. Saber Nagua B. Burham Salah S. Massoud 《Transition Metal Chemistry》2010,35(5):613-619
Two thiocyanato-Cu(II) complexes including mononuclear dithiocyanato Cu(Me3dpt)(NCS)2 (1) and the polymeric 1D [Cu(d,l-Ala)(μN,S–NCS)(H2O)]
n
(2) were synthesized and structurally characterized (Me3dpt = bis(N-methyl-3-propyl)methylamine, Ala = alaninate anion). The IR spectrum of complex 1 confirmed the N-bonding coordination mode of the thiocyanate groups, and its visible spectrum revealed the square pyramidal
geometry around the central Cu2+ ion. Single X-ray crystallography of 1 showed that the Cu(II) center displays square pyramidal geometry with severe distortion toward trigonal bipyramidal environment. Complex 2 forms a 1-D polymeric chain with the NCS− acting as a μN,S-ligand. A distorted SP geometry around the Cu2+ centers was achieved by the O and N atoms of alaninato anion, the aqua ligand and by the N and S atoms of the bridging thiocyanate
groups. Hydrogen bonds of the type N–H···O, N–H···S and O–H···O are formed in this complex leading to the extension of the
1D chain to a supramolecular network. 相似文献
14.
Jing-Xin Meng Xiao-Lan Wang En-Bo Wang Hai Fu Yan Zhong 《Transition Metal Chemistry》2009,34(3):361-366
Three new organic–inorganic hybrid compounds H[CuI(dafo)2]3{[CuI(dafo)2]2P2W18O62} · H2O (1), [CuI(dafo)2]3PMo12O40 (2) and [CuI(dafo)2]4SiW12O40 (3) (dafo = 4, 5-diazafluoren-9-one) have been hydrothermally synthesized and characterized by IR, TG and CV. Compound 1 exhibits a 3D supramolecular framework based on weak interactions between bisupported Dawson structure P2W18O62
6− units and copper-complex fragments. With the aid of π–π stacking and hydrogen bonding interactions, a 1D supramolecular framework
accommodating polyoxometalate (POM) anions is generated in 2. Compound 3 has similar fundamental units as 2, but the units are assembled in a different way. The distinction of their structures indicates that the POMs are the key
factor in determining the frameworks of the final products. The electrochemical properties of these compounds have been studied
using bulk-modified carbon paste electrodes.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
15.
Wen-Kui Dong Jun-Feng Tong Yin-Xia Sun Jian-Chao Wu Jian Yao Shang-Sheng Gong 《Transition Metal Chemistry》2010,35(4):419-426
Two new mono- and dinuclear Cu(II) complexes, namely [CuL1]·0.5H2O (1) and [(Cu2(L2)2)(DMF)]·0.5DMF (2) (H2L1 = 1,2-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)]methylene-aminooxy}ethane; H2L2 = 1,3-bis{[(Z)-(3-methyl-5-oxo-1-phenyl-1H-pyrazolidin-4(4H)-yl)(phenyl)] methyleneaminooxy}propane), have been synthesized and characterized by X-ray crystallography. The unit cell
of complex 1 contains two crystallographically independent but chemically identical [CuL1] molecules and one crystalline water molecule, showing a slightly distorted square-planar coordination geometry and forming
a wave-like pattern running along the a-axis via hydrogen bonding and π···π stacking interactions. Complex 2 has a dinuclear structure, comprising two Cu(II) atoms, two completely deprotonated phenolate bisoxime (L2)2− moieties (in the form of enol), and both coordinated and hemi-crystalline DMF molecules. Complex 2 has square-planar and square-pyramidal geometries around the two copper centers, whose basic coordination planes are almost
perpendicular and form an infinite three-dimensional supramolecular network structure involving intermolecular C–H···N, C–H···O,
and C–H···π(Ph) hydrogen bonding and π···π stacking interactions of neighboring pyrazole rings. 相似文献
16.
Two new neodymium complexes, [Nd2(abglyH)6(2,2′-bipy)2(H2O)2] · 4H2O 1 and {[Nd(abglyH)3(H2O)2] · (4,4′-bipy) · 7H2O}n
2 (abglyH2 = N-P-acetamidobenzenesulfonyl-glycine acid, 2,2′-bipy = 2,2′-bipyridine, 4,4′-bipy = 4,4′-bipyridine), have been synthesized and
their structures have been measured by X-ray crystallography. In 1, nine-coordinated Nd(III) ions are bridged by two syn–syn bidentate and two tridentate bridging carboxylate groups from four different abglyH− anions to form dinuclear motifs, which are further connected into a 3-D supramolecular framework via hydrogen bonds between
the binuclear motifs and the uncoordinated water molecules. In 2, eight-coordinated Nd(III) ions are linked by six carboxylate groups adopting a syn–syn bidentate bridging fashion to form a 1-D inorganic–organic alternating linear chain. These polymeric chains generate microchannels
extending along the a direction, and these cavities are occupied by discrete tetradecameric water clusters, which interact with their surroundings
and finally furnish the 3-D supramolecular network via hydrogen bonds. At the same time, π–π stacking interactions between
benzene rings from abglyH− anions also play an important role in stabilizing the network. 相似文献
17.
Chang-Xue An Xin-Li Han Peng-Bang Wang Zhi-Hui Zhang Hai-Ke Zhang Zhi-Jin Fan 《Transition Metal Chemistry》2008,33(7):835-841
Abstract Two new complexes, [Ag(L)2](NO3) · (H2O) (1) and [Co(L)2Cl2] (2) [L = 1-(imidazol-1-yl-methyl)-benzotriazole], have been synthesized and structurally characterized by X-ray diffraction techniques.
In complex (1), the Ag(I) atom adopts a linear coordination geometry involving the imidazole nitrogens of two ligands. The [Ag(L)2] units are developed into a three-dimensional structure by intermolecular hydrogen bonds, π–π interactions, and Ag···O interactions.
In complex (2), the Co(II) atom is in a distorted tetrahedral environment with two imidazole nitrogens and two chloride ligands. The [Co(L)2Cl2] units are assembled into a three-dimensional structure by intermolecular hydrogen bonds and π–π interactions. The bioactivities
of both complexes have been studied, and the results indicate that complex (1) exhibits excellent radical-scavenging (RS) and fungicidal (FG) activities while complex (2) only has weak fungicidal activity.
Graphical abstracts
Synthesis, crystal structures and biological activities of silver(I) and cobalt(II) complexes with an azole derivative ligand.
Chang-Xue An, Xin-Li Han, Peng-Bang Wang, Zhi-Hui Zhang*, Hai-Ke Zhang and Zhi-Jin Fan
Two novel complexes, [Ag(L)2](NO3) · (H2O) (1) and [Co(L)2Cl2] (2) [L = 1-(imidazol-1-yl-methyl)-benzotriazole] have been synthesized and structurally characterized. The molecules of complexes
(1) and (2) are extended to 2-D and 3-D structures by the non-coordinated bonds. The ligand and complex (1) exhibit excellent radical-scavenging and fungicidal activities.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
18.
Xing Chen Wen-Tao Yin Qian Huang Hong-Rong Zuo Jia-Rong Zhou Lin-Liang Yu Chun-Lin Ni Xue-Lei Hu 《Transition Metal Chemistry》2010,35(2):143-149
Two new salts, [BzTPP]2[Cu(mnt)2] (1) and [4NO2BzTPP]2[Cu(mnt)2] (2) (BzTPP+ = benzyltriphenylphosphonium and mnt2− = maleonitriledithiolate) have been prepared and characterized by elemental analyses, UV, IR, molar conductivity and single-crystal
X-ray diffraction. The single-crystal structure analysis shows that 1 crystallizes in the monoclinic space group P21/n, while 2 crystallizes in the triclinic space group P−1. The effects of weak intramolecular interactions such as C–H···O, C–H···S, C–H···N, C–H···Cu hydrogen bonds and p···π, π···π stacking interactions in the solids generate a 3D network structure. It is noted that the change in the molecular
topology of the counteraction when the 4-substituted group in the benzyl ring is changed from H to NO2 results in differences in the crystal system, space group, weak interactions and the stacking mode of the cations and anions
of 1 and 2. The magnetic susceptibilities of these salts measured in the temperature range 2.0 to 300 K show weak ferromagnetic coupling
features with θ = 2.05 × 10−2 K for 1 and 5.13 × 10−3 K for 2. 相似文献
19.
A Schiff base ligand containing thiocarbamide group of 4-phenyl-1-(4-methoxyl-1-phenylethylidene)thiosemicarbazide (HL) and
its three mononuclear metal complexes of ZnL2 (1), NiL2 (2), and CuL2 (3) have been synthesized. Elemental analysis, IR, and X-ray single crystal diffraction characterizations for the ligand and
the three complexes have been carried out. In the three complexes, the central metallic ions of Zn2+, Ni2+, and Cu2+ coordinate with two deprotonated ligands of L−, respectively. In 1, Zn2+ ion adopts a distorted tetrahedral geometry, while in 2 and 3, both the Ni2+ and Cu2+ ions possess distorted square planar configurations. For the four compounds, UV–Vis spectra have been measured and DFT calculations
at B3LYP/LANL2DZ level of theory prove that the electronic spectra of HL and 1 are corresponding with electronic transitions of n → π* and π → π* in the ligand itself and the electronic spectra of 2 and 3 are attributed to intraligand electronic transitions as well as d–d electronic transitions. Electrochemical investigations reveal that the different metal–ligand interactions have changed the
peak shapes and peak locations, which are corresponding with the DFT-B3LYP/LANL2DZ calculational results. Fluorescence spectra
measurements indicate that the ligand emits purple fluorescence and the complex 1 emits stronger blue fluorescence, while the complexes 2 and 3 quench fluorescence. The thermal analyses result show that the three complexes undergo two similar decomposition processes
because of their similar geometric configurations. 相似文献
20.
Abstract Reactions of monovacant Dawson-/Keggin-polyoxoanions, formed in situ from trivacant Dawson-/Keggin-precursors, with copper
complexes under hydrothermal conditions lead to three inorganic–organic hybrid polyoxotungstates [Cu(en)2(H2O)]2{[Cu(en)2(H2O)]2[Cu(en)2]4[Cu(en)2][α2-P2W17CuO61]2}·(OH)2·12H2O (1), [Cu(dap)2][Cu(dap)2(H2O)]2[α-PW11CuO39]·(OH)·2H2O (2) and (H2en)2[α-PW11CuO39][Cu(en)2(H2O)2]0.5·1.5H2O (3) (en = ethylenediamine and dap = 1,2-diaminopropane). X-ray structural analyses demonstrate that 1 exhibits the first zigzag 1-D chain arrangement constructed from mono-copperII-substituted Dawson dimeric polyoxoanions [α2-P2W17CuO61]216− linked by [Cu(en)2]2+ bridges, whereas 2 and 3 display 1-D linear chain architectures made up of mono-copperII-substituted Keggin polyoxoanions [α-PCuW11O39]5− linked together via corner-sharing MO6 octahedra (M = Cu or W).
Graphical Abstract Reactions of monovacant Dawson or Keggin polyoxoanions with copper complexes under hydrothermal conditions lead to three novel
1-D chain-like inorganic- organic hybrid polyoxotungstates.
相似文献