Bis(1,10‐phenanthroline‐κ2N,N′)(squarato‐κO)copper(II) trihydrate

The title mononuclear [Cu(sq)(phen)₂]·3H₂O complex [sq is squarate (C₄O₄) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)] has been synthesized and the structure consists of a neutral mononuclear [Cu(sq)(phen)₂] unit and three solvate water mol­ecules. The Cu^II ion has distorted square‐pyramidal coordination geometry, comprised of one carboxyl­ate O atom from a monodentate squarate ligand and four N atoms from two chelating phen ligands. An extensive three‐dimensional network of OW—H⋯O/OW hydrogen bonds, face‐to‐face π–­π interactions between the 1,10‐phenanthroline aromatic rings and a weak π–ring interaction are responsible for crystal stabilization.     

Tetranuclear and One‐dimensional Cobalt Complexes with 5‐tert‐Butyl Isophthalic Acid and Chelating Neutral Ligands

Two new Co^II coordination polymers [Co₄(tbip)₄(bipy)₄(H₂O)₄] ( 1 ) and [Co(tbip)(phen)(H₂O)] · H₂O ( 2 ) (H₂tbip = 5‐tert‐butyl isophthalic acid, bipy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Compound 1 is a tbip‐bridged tetranuclear cobalt(II) complex, which is further linked by hydrogen bonds to form a supramolecular network. Compound 2 shows a tbip‐bridged linear chain structure, which is extended by hydrogen bonds to generate a double chain. Magnetic measurements show that there are weak ferromagnetic interactions between the adjacent Co^II ions in 1 .     

Synthesis,Structures, and Fluorescent Properties of Three Cobalt‐Based Coordination Polymers with a Rigid Tripodal Carboxylate Ligand

Three cobalt(II) coordination polymers, [Co₂(tatb)₂(2,2′‐bipy)₂ (H₂O)₂ · DMA · 2H₂O] ( 1 ), [Co₂(tatb)₂(1,10‐phen)₂(H₂O)₂ · 2H₂O] ( 2 ) and [Co(tatb)(1,3‐dpp) · H₂O] ( 3 ) (H₃tatb = 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl; 1,10‐phen = 1,10‐phenanthroline; 1,3‐dpp = 1,3‐bis(pyridin‐4‐yl)propane), were synthesized solvothermally and characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double‐chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π–π interactions. Complex 3 possesses 2D 4⁴‐sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1 , 2 and 3 were also investigated.     

A Polymeric Arched Chain and a Chair‐like M2L2‐Metallamacrocycle Crystal Engineered of [M(phen)]2+ (M = Cu,Cd; phen = 1,10‐Phenanthroline) Corner Units and the Bent Ligand 4,4′‐Dithiodipyridine

Self‐assembly of Cd(phen)²⁺ and Cu(phen)²⁺ (phen = 1,10‐phenanthroline) building blocks with the bent ligand 4,4′‐dithiodipyridine (dtdp) has been investigated. Both building blocks serve as corner units with constrained cis‐geometry. The arched chain coordination polymer [{Cd(phen)(μ‐dtdp)(dtdp)(H₂O)}(ClO₄)₂·2CH₃OH·1.5H₂O]_n ( 1 ) crystallised from a mixture of Cd(ClO₄)₂·H₂O, phen and dtdp in methanol. The reaction of [Cu(phen)(H₂O)₂](CF₃SO₃)₂ ( 2 ) with dtdp in an ethanol/water mixture yielded a chair‐like metallamacrocycle, [{Cu(phen)(CF₃SO₃)₂}₂(μ‐dtpd)₂] ( 3 ). The crystal structure of the precursor complex 2 is also reported.     

Tetra­aqua(1,10‐phenanthroline‐κ2N,N′)­manganese(II) sulfate dihydrate

The title compound, [Mn(C₁₂H₈N₂)(H₂O)₄]SO₄·2H₂O, was obtained unexpectedly as a by‐product from the reaction of sodium maleate, 1,10‐phenanthroline (phen) and manganese sulfate tetrahydrate. The Mn atom is coordinated by the two N atoms of the phen ligand and four water O atoms in a highly distorted octahedral geometry, with Mn—O distances in the range 2.155 (2)–2.203 (2) Å and Mn—N distances of 2.254 (2) and 2.272 (3) Å. Extensive hydrogen‐bonding interactions involving the water mol­ecules and sulfate anions, and stacking interactions involving the phen rings, are observed in the crystal structure.     

Crystallographic report: Diaquabis(1,10‐phenanthroline)zinc(II) 4,5‐dihydroxy‐1,3‐benzenedisulfonate trihydrate

The zinc atom has a distorted octahedral geometry defined by two 1,10‐phenanthroline and two cis water molecules. A three‐dimensional network structure arises owing to extensive hydrogen bonds involving all the components of [Zn(phen)₂(H₂O)₂][C₆H₂(OH)₂(SO₃)₂]·3H₂O. Copyright © 2005 John Wiley & Sons, Ltd.     

多吡啶锌配合物键合与切割DNA研究

The complex of Zn[(phen)(dione)Cl]ClO_4·H_2O(where phen is 1,10-phenanthroline and dione is 1,10-phenan-throline-5,6-dione)has been synthesized and characterized.The interaction of the complex with DNA was investi-gated using UV absorption,fluorescence spectroscopy and electrophoresis measurements.The results show that thecomplex mainly binds to the double helix of DNA with intercalation mode and the binding constant K is 2.4×10~4mol~(-1)·L.Moreover,the complex can efficiently cleave plasmid DNA at physiological pH and temperature.Thecleavage occurs via a hydrolysis mechanism,which is showed by adding radical scavengers,rigorously anaerobicexperiments,analysis for malondialdehyde-like products,and the hydrolysis experiment of BDNPP with a rate con-stant k_(obs)of 5.3×10~(-6)s~(-1).     

Synthesis,Characterization, and Crystal Structure of a Chromium(III)‐Complex Containing 2,6‐Pyridinedicarboxylic Acid and 1,10‐Phenanthroline

The reaction of solution 2,6‐pyridinedicarboxylic acid and 1,10‐phenanthroline ( 1 ) with CrCl₃·6H₂O led to the complex [Cr(phen)(pydc)(H₂O)][Cr(pydc)₂]·4H₂O ( 2 ) (phen is 1,10‐phenanthroline and pydcH₂ is 2,6‐pyridinedicarboxylic acid). 2 was characterized by elemental analysis, IR spectroscopy and single‐crystal structure determination. Crystal data for 2 at ?80 °C: triclinic, space group , a = 818.5(1), b = 1492.2(1), c = 1533.6(2) pm, α = 76.45(1)°, β = 84.22(1)°, γ = 77.99(1)°, Z = 2, R₁ = 0.0416.     

Bis(μ‐2‐sulfonatobenzoato)bis[(1,10‐phenanthroline)­lead(II)] dihydrate

In the title centrosymmetric dimer, [Pb₂(sbc)₂(phen)₂]·2H₂O [sbc is the 2‐sulfonatobenzoate dianion (C₇H₄O₅S) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], each Pb^II ion is six‐coordinated by four O atoms, viz. carboxyl­ate and sulfonate O atoms from two sbc anions, and two N atoms from a 1,10‐phenanthroline ligand. One 1,10‐phenanthroline ligand and the carboxyl­ate group of one sbc ligand are chelated to each Pb^II cation, and the sulfonate group of the other sbc unit is monodentate. One O atom of the chelated carboxyl­ate group also bridges to the other Pb^II cation, so that each pair of Pb^II ions is bridged by two sbc anions and has the same coordination environment, forming a dinuclear ring. Each pair of Pb^II ions is thus connected by two different kinds of bridges, namely a carboxyl­ate short bridge and a carboxyl­ate–sulfonate long bridge. There is also a special position of site symmetry at the centre of the two Pb^II cations.     

Cadmium(II) Complexes with Mixed cis‐Epoxysuccinate and 2,2′‐Bipyridyl‐Like Ligands: Syntheses,Crystal Structures,and Luminescent Properties

Two new Cd^II complexes, [Cd( ces )(phen)]_∞ ( 1 ) and {[Cd( ces )(bpy)(H₂O)](H₂O)}₂ ( 2 ), were prepared by slow solvent evaporation methods from mixtures of cis‐epoxysuccinic acid and Cd(ClO₄)₂ · 6H₂O in the presence of phen or bpy co‐ligand ( ces = cis‐epoxysuccinate, phen = 1,10‐phenanthroline, and bpy = 2,2′‐bipyridine). Single‐crystal X‐ray diffraction analyses show that complex 1 has a one‐dimensional (1D) helical chain that is further assembled into a two‐dimensional (2D) sheet, and then an overall three‐dimensional (3D) network by the interchain C–H ··· O hydrogen bonds. Complex 2 features a dinuclear structure, which is further interlinked into a 3D supramolecular network by the co‐effects of intermolecular C–H ··· O and C–H ··· π hydrogen bonds as well as π ··· π stacking interactions. The structural differences between 1 and 2 are attributable to the intervention of different 2,2′‐bipyridyl‐like co‐ligands. Moreover, 1 and 2 exhibit intense solid‐state luminescence at room temperature, which mainly originates from the intraligand π→π* transitions of aromatic co‐ligands.     

Two Self‐assembled Water Clusters Stabilized by Cu‐containing Compounds Based on MoO42–

Two copper‐containing compounds based on MoO₄^2–, [Cu₄(phen)₄(μ₂‐OH)₂(μ₃‐OH)₂(H₂O)₂][MoO₄]₂ · 10H₂O ( 1 ) and [Cu(phen)₂Mo₂O₇(phen)] · 8H₂O ( 2 ) (phen = 1,10‐phenanthroline), were hydrothermally synthesized. In the crystal lattices of 1 and 2 , discrete octameric water cycles and 2D layer water clusters were observed. The cyclic water octamer clusters exist stably in the channels constructed by [Cu₄(phen)₄(OH)₄(H₂O)₂]²⁺ and MoO₄^2– by hydrogen bonds in 1 at low temperature and 2D layer water clusters are formed by (H₂O)₁₆ units in 2 .     

含有二十分子水簇的金属—水二维网的构成

以醋酸铜、1,10-邻菲啰啉和顺丁烯二酸在去离子水和乙醇的混合溶液中反应得到了配合物单晶[Cd(phen)2(male)(H2O)]·9.5H2O (1) (phen＝1,10－邻菲啰啉; H2male＝顺丁烯二酸)。采用元素分析、红外光谱和热重分析对化合物进行了表征。用X－射线单晶衍射分析了晶体结构,结果表明：在化合物１中存在着由二十分子水簇构成的结构新颖的一维水链。一维水链和[Cd(phen)2(male)(H2O)]依靠氢键作用构成了独特的包含金属－水网的二维结构。     

Synthesis,Crystal Structures and Properties of Tetrametallic Complexes: [M2(phen)4(FCA)2](ClO4)2·(H2O)2 (M=Zn or Co,phen=1,10‐phenanthroline,FCA=anion of 3‐ferrocenyl‐2‐crotonic acid)

Two new complexes [Zn₂(phen)₄(FCA)₂](ClO₄)₂·(H₂O)₂ ( 1 ) and [Co₂(phen)₄ (FCA)₂](ClO₄)₂·(H₂O)₂ (2) (FCA=anion of 3‐ferrocenyl‐2‐crotonic acid, phen=1,10‐phenanthroline) have been synthesized, and characterized by elemental analysis, IR, UV‐Vis spectra, thermal analyses, and single‐crystal X‐ray diffraction. Two M(II) (M=Zn or Co) ions are bridged by two FCA anions with syn‐anti bridging ligands, leading to dimeric cores, [M₂(phen)₄(FCA)₂]²⁺, and each M(II) ion is six‐coordinated in a distorted octahedral geometry by two chelate phen ligands and two μ₂‐carboxylate oxygen atoms from two FCA groups. The M(II)…M(II) intradimer distances are 0.4391 and 0.4462 nm in 1 and 2 , respectively. Electrochemical properties of the complexes have been discussed.     

Cadmium(II) Complexes with a Bulky Anthracene‐based Carboxylate Ligand: Syntheses,Crystal Structures,and Luminescent Properties

To explore the coordination possibilities of anthracene‐based ligands, three cadmium(ιι) complexes with anthracene‐9‐carboxylate ( L ) and relevant auxiliary chelating or bridging ligands were synthesized and characterized: Cd₂( L )₄(2bpy)₂(μ‐H₂O) ( 1 ), Cd₂( L )₄(phen)₂(μ‐H₂O) ( 2 ), and {[Cd₃( L )₆(4bpy)]}_∞ ( 3 ) (2bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline, and 4bpy = 4,4′‐bipyridine). Structural analyses show that complexes 1 and 2 both take dinuclear structures by incorporating the chelating 2bpy or phen ligand, which are further interlinked by intermolecular hydrogen‐bonding, π ··· π stacking, and/or C–H ··· π supramolecular interactions to generate higher‐dimensional supramolecular frameworks. Complex 3 has a one‐dimensional (1D) ribbon‐like structure, which is further assembled into a two‐dimensional (2D) layer, and a three‐dimensional (3D) framework by the co‐effects of interchain C–H ··· O hydrogen‐bonding and C–H ··· π supramolecular interactions. Moreover, the luminescent properties of these complexes were further investigated in detail.     

An extended two‐dimensional copper–molybdate compound with mixed dicarboxyl and organodiamine ligands

The title complex, poly[di‐μ₃‐oxo‐hepta‐μ₂‐oxo‐tetra­oxo­bis(1,10‐phenanthroline)‐μ₄‐terephthalato‐dicopper(II)­tetra­molybdate(VI)], [Cu₂Mo₄(C₈H₄O₄)O₁₃(C₁₂H₈N₂)₂], represents a novel two‐dimensional copper–molybdate compound with mixed ligands. Tetra­nuclear molybdenum oxide clusters are joined through corner‐sharing into a ribbon‐like chain, with [Cu(phen)]²⁺ (phen is 1,10‐phenanthroline) complexes grafted onto either side. The terephthalate ligand lies about an inversion centre and links these chains to form a layer via Cu—O and Mo—O bonds. Face‐to‐face π–π stacking inter­actions between adjacent phen ligands stabilize the structure.     

Diaquabis(2,5‐dihydroxybenzoato‐κO)bis(1,10‐phenanthroline‐κ2N,N′)strontium(II) bis(1,10‐phenanthroline) tetrahydrate

The title compound, [Sr(C₇H₅O₄)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₁₂H₈N₂·4H₂O, consists of an Sr^II complex, uncoordinated phenanthroline (phen) molecules and solvent water molecules. The Sr^II ion is located on a twofold axis and is coordinated by two phen ligands, two dihydroxybenzoate anions and two water molecules in a distorted tetragonal antiprismatic geometry. Partially overlapped arrangements exist between parallel coordinated and parallel uncoordinated phen rings; the face‐to‐face separations between the former (coordinated) and the latter (uncoordinated) rings are 3.436 (13) and 3.550 (14) Å, respectively. This difference suggests the effect of metal coordination on π–π stacking between phen rings.     

Synthesis,Characterization, Antibacterial and Antifungal Activity of Yttrium(III) Complexes Including 1,10‐Phenanthroline

Two rare metal coordination complexes of yttrium(III) including 1,10‐phenanthroline, Y(phen)₂(NO₃)₃ and (phenH)₂[Y₂(pydc)₃(NO₃)₂·6H₂O] (phen=1,10‐phenanthroline, pydc=2,6‐pyridinedicarboxylate), and a proton transfer compound (phenH⁺)₂(pydc^2?) were synthesized and characterized by elemental analysis, molar conductance, infrared spectra (IR), nuclear magnetic resonance (NMR) and thermal analysis. The proposed structures of yttrium complexes were exhibited. The in vitro biological activities of the newly synthesized complexes have also been investigated against Bacillus coli, Staphylococcus aureus and Candida albicans. The results showed that yttrium(III) complexes including 1,10‐phenanthroline exhibited better antibacterial/antifungal activity than their ligands and corresponding compounds.     

Two Uranyl Complexes with Pyromellitic Acid. A Heterometallic Complex with U=O–CuII Interaction

Two uranyl complexes based on pyromellitic acid were hydrothermally synthesized, and their X‐ray single‐crystal diffraction structures were determined. Complex [UO₂(Hbtec)]^–(Himd)⁺ · H₂O ( 1 ) (H₄btec = pyromellitic acid, imd = imidazole), is an ionic complex, which shows a typical (4, 4) topological structure in the space. A heterometallic complex, UO₂Cu(btec)(phen) ( 2 ) (phen = 1,10‐phenanthroline) results from the reaction of uranyl nitrate and copper(II) bromide with pyromellitic acid. The structure of complex 2 revealed that the chains of UO₇ and CuO₃N₂ units were connected to each other through the carboxyl groups and U=O–Cu interactions to create a two‐dimensional framework.     

Non-isothermal Kinetics of the First-stage Decomposition Reaction of the Complex of Terbium p-Methylbenzoate with 1,10-Phenanthroline

The thermal behavior of Tb₂ (p‐MBA)₆(phen)₂ (p‐MBA=p‐methylbenzoate; phen=1,10‐phenanthroline) in a static air atmosphere was investigated by TG‐DTG, SEM and IR techniques. The thermal decomposition of the Tb₂(p‐MBA)₆(phen)₂ occurred in three consecutive stages at T_P of 354, 457 and 595 °C. By Malek method, RO (n<1) was defined as kinetic model for the first‐step thermal decomposition. The activation energy (E) of this step is 170.21 kJ·mol^‐1, the enthalpy of activation (ΔH^≠) 164.98 kJ·mol^‐1, the Gibbs free energy of activation (ΔG^≠) 145.04 kJ·mol^‐1, the entropy of activation (ΔS^≠) 31.77 J·mol^‐1·K^‐1, and the pre‐exponential factor (A) 10^15.21 s^‐1.     

Synthesis,Charactarization and Crystal Structures of Lanthanide Phenoxyacetate Complexes with1,10—Phenanthroline

Three new lanthanide phenoxyacetate complexes with 1,10‐phenanthroline. [Nd(POA)₃ (phen)]₂ · 2C₂H₅OH (1), [Eu(POA)₃‐ (phen)]₂ · 2C₂H₅OH (2) and [Sm(POA)₂(DMSO)(phen)]₂‐ (ClO₄)₂ (3) (POA= phenoxyacetate, phen = 1,10‐phenanthroline, DMSO = dimethyl sulfoxide), were synthesized and characterized by elemental analyses, IR, UV‐vis and FAB‐MS spectra. Their structures were determined by single crystal X‐ray diffraction analysis. In complexes 1 and 2, the carboxylate groups are bonded to Ln³⁺ ion in three modes: the chelating bidentate, the bridging bidentate and the bridging tridentate. In complex 3, the carboxylate groups are bonded to Sm³⁺ ion only involved in one mode: the bridging bidentate. The luminescence behavior of complex 2 was also studied by means of emission spectra.