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1.
Two manganese(II) bipyridine carboxylate complexes, [(bipy)2MnII(μ‐C2H5CO2)2MnII(bipy)2}2](ClO4)2 ( 1 ), and [MnII(ClCH2CO2)(H2O)(bipy)2]ClO4 · H2O ( 2 ) were prepared. 1 crystallizes in the triclinic space group P 1 with a = 8.604(3), b = 12.062(3), c = 13.471(3) Å, α = 112.47(2), β = 93.86(2), γ = 92.87(3)°, V = 1211.1(6) Å3 and Z = 1. In the dimeric, cationic complex with a crystallographic center of symmetry two 2,2′‐bipyridine molecules chelate each manganese atom. These two metal fragments are then bridged by two propionato groups in a syn‐anti conformation. The Mn…Mn distance is 4.653 Å. 2 crystallizes in the monoclinic space group P21/c with a = 9.042(1), b = 13.891(1), c = 21.022(3) Å, β = 102.00(1)°, V = 2569.3(5) Å3 and Z = 4. 2  is a monomeric cationic complex in which two bipyridine ligands chelate the manganese atom in a cis fashion. A chloroacetato and an aqua ligand complete the six‐coordination. Only in 2 is the intermolecular packing controlled by weak π‐stacking besides C–H…π contacts between the bipyridine ligands.  相似文献   

2.
The mononuclear compounds [Cu(OAc)(bipy)2]Cl·4H2O·1/2MeOH( 1 ) and [Co(OH2)2(phen)2](OAc)2·6H2O( 2 ) were unexpectedly obtained as single crystals from mother liquors left following isolation of the expected products of the reactions, in ethanol of Cu(OAc)2, benzylic acid and 2, 2'‐bipyridine (for 1 ) and Co(OAc)2, D, L‐mandelic acid and 1, 10‐phenanthroline (for 2 ). The complexes were characterized by elemental analysis, IR and electronic spectroscopy and magnetic measurements at room temperature and their structures were determined by single‐crystal X‐ray analysis. In 1 , the pentacoordinated copper atom has a basically square pyramidal coordination polyhedron, while in 2 the cobalt atom has a distorted octahedral environment. In both cases, the complexes are linked by hydrogen bonds and aromatic‐aromatic interactions.  相似文献   

3.
The single crystal X‐ray analysis of a novel thiophene‐2,5‐dicarboxylic acid (H2Tda) Manganese(II) coordination polymer, {Mn23‐Tda)2(μ‐H2O)(H2O)2(bipy)]·DMF}n, shows two different types of Mn2+‐ions with environment of Mn1O6 and Mn2O4N2, and the complex is a two‐dimensional polymer as a result of bridging (Tda)2? ligands and by connecting the carboxylate‐ and water‐bridged {Mn2(μ‐Tda)2(μ‐H2O)} nodes.  相似文献   

4.
Reaction of O,O′‐diisopropylthiophosphoric acid isothiocyanate (iPrO)2P(S)NCS with 1,10‐diaza‐18‐crown‐6, 1,7‐diaza‐18‐crown‐6, or 1,7‐diaza‐15‐crown‐5 leads to the N‐thiophosphorylated bis‐thioureas N,N′‐bis[C(S)NHP(S)(OiPr)2]‐1,10‐diaza‐18‐crown‐6 ( H2LI ), N,N′‐bis[C(S)NHP(S)(OiPr)2]‐1,7‐diaza‐18‐crown‐6 ( H2LII ) and N,N′‐bis[C(S)NHP(S)(OiPr)2]‐1,7‐diaza‐15‐crown‐5 ( H2LIII ). Reaction of the potassium salts of H2LI–III with a mixture of CuI and 2,2′‐bipyridine ( bpy ) or 1,10‐phenanthroline ( phen ) in aqueous EtOH/CH2Cl2 leads to the dinuclear complexes [Cu2(bpy)2LI–III] and [Cu2(phen)2LI–III] . The structures of these compounds were investigated by 1H, 31P{1H} NMR spectroscopy, and elemental analysis. The crystal structures of H2LI and [Cu2(phen)2LI] were determined by single‐crystal X‐ray diffraction. Extraction capacities of the obtained compounds in comparison to the related compounds 1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(=CMe2)CH2P(O)(OiPr)2]‐1,10‐diaza‐18‐crown‐6, N,N′‐bis[C(S)NHP(O)(OiPr)2]‐1,10‐diaza‐18‐crown‐6 towards the picrate salts LiPic, NaPic, KPic. and NH4Pic were also studied.  相似文献   

5.
A novel 1D polymeric lead(II) complex containing the first Pb2‐(μ‐N3)2 motif, [Pb(phen)(μ‐N3)(μ‐NO3)]n (phen = 1,10‐phenanthroline), has been synthesized and characterized. The single‐crystal X‐ray data showed the coordination number of Pb2+ ions to be eight (PbN4O4) with the Pb2+ ions having “stereo‐chemically active” electron lone pairs; the coordination sphere is hemidirected. The chains interact with each other via π‐π interactions to create a 3D framework.  相似文献   

6.
Two new lead(II) complexes containing nitrite, [Pb(L)2(NO2)2], L?=?1,10-phenanthroline (phen) or 2,2′-bipyridine (bpy), have been synthesized and characterized. The crystal structure of [Pb(phen)2(NO2)2] shows monomeric units. The coordination number is eight (four from “phen” ligands and four nitrite anions), weak interaction of lead(II) with oxygen atoms of adjacent molecules produce dimer units in the solid state. The arrangement of ligands exhibits a coordination hole around the lead(II), occupied possibly by a stereoactive lone pair of electrons on lead(II), and the coordination around lead is hemidirected. There is a π–π stacking interaction between the parallel aromatic rings that may help to increase the “gap” around lead(II).  相似文献   

7.
The compound [Cu42‐OH)23‐OH)2Cl2(bipy)4]Cl2 · 6H2O ( 1 ) was obtained by recrystallization of [Cu(HB)2(2, 2′‐bipy)] · H2O (H2B = diphenylglycolic acid) from EtOH/CH2Cl2 and their structure has been determined by single‐crystal X‐ray analysis. The cationic complex may be described as based on a Cu4(OH)4 core with a “stepped cubane” structure. The coordination polyhedron around each copper is a distorted square pyramid. The tetranuclear units are linked in the crystal by C‐H…Cl hydrogen bonds and by π‐π interactions between bipyridine rings. IR data are also presented.  相似文献   

8.
The ligand pteridino[6,7‐f] [1,10]phenanthroline‐11,13‐diamine (ppn) and its RuII complexes [Ru(bpy)2(ppn)]2+ ( 1 ; bpy=2,2′‐bipyridine) and [Ru(phen)2(ppn)]2+ ( 2 ; phen=1,10‐phenanthroline) were synthesized and characterized by elemental analysis, electrospray MS, 1H‐NMR, and cyclic voltammetry. The DNA‐binding behaviors of 1 and 2 were studied by spectroscopic and viscosity measurements. The results indicate that both complexes strongly bind to calf‐thymus DNA in an intercalative mode, with DNA‐binding constants Kb of (1.7±0.4)?106 M ?1 and (2.6±0.2)?106 M ?1, respectively. The complexes 1 and 2 exhibit excellent DNA‐‘light switch’ performances, i.e., they do not (or extremely weakly) show luminescence in aqueous solution at room temperature but are strongly luminescent in the presence of DNA. In particular, the experimental results suggest that the ancillary ligands bpy and phen not only have a significant effect on the DNA‐binding affinities of 1 and 2 but also have a certain effect on their spectral properties. [Ru(phen)2(ppn)]2+( 2 ) might be developed into a very prospective DNA‐‘light switch’ complex. To explain the DNA‐binding and spectral properties of 1 and 2 , theoretical calculations were also carried out applying the DFT/TDDFT method.  相似文献   

9.
The two complexes of composition Cu2(OAc)4(phen)(H2O)2 ( 1 ) andCu2(OAc)4(phen)2(H2O) ( 2 ) have been synthesized and characterized by chemical analysis and IR and electronic spectroscopies. Compound 2 has the structure of a dimer with a phenanthroline molecule and two monodentate acetate groups coordinated to each copper atom and a water molecule as the only bridging ligand between them. Each copper atom has a distorted square‐planar pyramidal coordination, determined by two oxygen atoms at 1.94(3) and 1.959(3) Å, two nitrogen atoms at 2.023(4) Å and the oxygen atom of the bridging water molecule at 2.289(2) Å. The distance between the two copper atoms is of 4.29 Å and the angle Cu(1)‐O(3)‐Cu(1A) 139.2(2)°. The water molecule is involved in two intramolecular hydrogen bonds with non coordinated oxygen atoms. The distance between the molecules of phenanthroline is 3.75 Å. Magnetic and EPR results for Cu2(OAc)4(phen)(H2O)2 ( 1 ), Cu2(OAc)4(phen)2(H2O) ( 2 ), Cu2(OAc)4(bipy) ( 3 ) and Cu2(OAc)4(bipy)2(H2O)2 ( 4 ) have been analysed and compared. For 1 and 3 an antiferromagnetic dimer unit [Cu2(μ‐OAc)4] with 2J = ?325 and ?292 cm?1, respectively, and other two copper atoms without significant magnetic interaction are present. Triplet signals are detected in the EPR spectra. In 2 and 4 there is no practically magnetic exchange and the orthorhombic signals are observed in the EPR spectra.  相似文献   

10.
The photoluminescence characteristics of the [Cd(bipy)3][PF6]2 complex are reported. A moderately large quantum yield (φ) of 1.07 × 10?2 is exhibited in acetonitrile solution at 298 K. Crystallography shows the dication to have a distorted octahedral geometry and the crystal structure to be stabilized by C? H···π and C? H···F interactions. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

11.
Two transition metal‐organic coordination polymers, [Mn2(1,3‐bdc)2(Me2bpy)2] · Me2bpy ( 1 ) and [Co(4,4′‐oba)(Me2bpy)] ( 2 ) were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, TG, and single‐crystal X‐ray diffraction [1,3‐H2bdc = benzene‐1,3‐dicarboxylic acid, H2oba = 4,4′‐oxybis(benzoic acid) Me2bpy = 4,4′‐dimethyl‐2,2′‐bipyridine]. Compound 1 crystallizes in the orthorhombic system, space group P212121, with a = 23.371(5), b = 14.419(3), and c = 14.251(3) Å. Compound 2 crystallizes in the monoclinic system, space group P21/c, with a = 7.4863(15), b = 18.272(4), c = 16.953(5) Å, and β = 107.44(3)°. The crystal structure of complex 1 is a wave‐like layer with central Mn2+ atoms bridged by 1,3‐bdc ligands, whereas the structure of compound 2 presents a ladder chain of hexacoordinate Co2+ atoms, in which the metal atoms are bridged by 4,4′‐oba ligands and decorated by Me2bpy ligands. The two compounds are further extended into 3D supramolecular structures through π–π stacking interactions. Additionally, the compounds show intense fluorescence in solid state at room temperature.  相似文献   

12.
Two coordination polymers, {[Zn2(L)(bpy)] · 2H2O}n ( 1 ) and [Zn2(L)(bpe)]n ( 2 ) [H4L = terphenyl‐2,2′,4,4′‐tetracarboxylic acid, bpy = 4,4′‐bipyridine, and bpe = 1,2‐bis(4‐pyridyl)ethane], were hydrothermally synthesized under similar conditions and characterized by elemental analysis, IR spectroscopy, TGA, and single‐crystal X‐ray diffraction analysis. Compound 1 has a 3D framework containing Zn–O–C–O–Zn 1D chains. Compound 2 exhibits a 3D framework, which features tubular channels. The channels are occupied by bpe molecules. The differences in the structures demonstrate that the auxiliary dipyridyl‐containing ligand has a significant effect on the construction of the final framework. Additionally, the fluorescent properties of the two compounds were also studied in the solid state at room temperature.  相似文献   

13.
Polysulfonylamines. CXVI. Destructive Complexation of the Dimeric Diorganyltin(IV) Hydroxide [Me2Sn(A)(μ‐OH)]2 (HA = Benzene‐1,2‐disulfonimide): Formation and Structures of the Mononuclear Complexes [Me2Sn(A)2(OPPh3)2] and [Me2Sn(phen)2]2⊕ · 2 A · MeCN Destructive complexation of the dimeric hydroxide [Me2Sn(A)(μ‐OH)]2, where A is deprotonated benzene‐1,2‐disulfonimide, with two equivalents of triphenylphosphine oxide or 1,10‐phenanthroline in hot MeCN produced, along with Me2SnO and water, the novel coordination compounds [Me2Sn(A)2(OPPh3)2] ( 3 , triclinic, space group P 1) and [Me2Sn(phen)2]2⊕ · 2 A · MeCN ( 4 , monoclinic, P21/c). In the uncharged all‐trans octahedral complex 3 , the heteroligands are unidentally O‐bonded to the tin atom, which resides on a crystallographic centre of inversion [Sn–O(S) 227.4(2), Sn–O(P) 219.6(2) pm, cis‐angles in the range 87–93°; anionic ligand partially disordered over two equally populated sites for N, two S and non‐coordinating O atoms]. The cation occurring in the crystal of 4 has a severely distorted cis‐octahedral C2N4 coordination geometry around tin and represents the first authenticated example of a dicationic tin(IV) dichelate [R2Sn(L–L′)2]2⊕ to adopt a cis‐structure [C–Sn–C 108.44(11)°]. The five‐membered chelate rings are nearly planar, with similar bite angles of the bidentate ligands, but unsymmetric Sn–N bond lengths, each of the longer bonds being trans to a methyl group [ring 1: N–Sn–N 71.24(7)°, Sn–N 226.81(19) and 237.5(2) pm; ring 2: 71.63(7)°, 228.0(2) and 232.20(19) pm]. In both structures, the bicyclic and effectively CS symmetric A ions have their five‐membered rings distorted into an envelope conformation, with N atoms displaced by 28–43 pm from the corresponding C6S2 mean plane.  相似文献   

14.
Two new ZnII(μ‐4,4′‐bipy) coordination polymers with acetate anions, [Zn(4,4′‐bipy)(AcO)2] ( 1 ) and [Zn2(4,4′‐bipy)(AcO)4] ( 2 ), have been synthesized. The compounds were characterized with elemental analysis, IR‐, 1H NMR‐, 13C NMR spectroscopy and studied by thermal analysis, fluorescence measurements and x‐ray crystallography. The structural studies of compound 1 suggest the structure is a coordination polymer of zinc(II) consisting of linear double chains formed by bridging 4,4′‐bipy ligand and connection of the acetate‐bridged centrosymmetric [Zn2(OAc)2]2+ nodes.  相似文献   

15.
Bipy, Phen, and P(C6H4CH2NMe2‐2)3 in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C6H4CH2NMe2‐2)3]AgOTf and [Ag(phen)2]OTf The reaction of [P(C6H4CH2NMe2‐2)3]AgX ( 1a , X = OTf; 1b , X = OClO3) with equimolar amounts of LcapL ( 2a , LcapL = 2, 2′‐bipyridine, bipy; 2b , LcapL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , LcapL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C6H4CH2NMe2‐2)3]Ag(LcapL)}+X (LcapL = bipy: 3a , X = OTf; 3b , X = ClO4; LcapL = bipy′: 3c , X = OTf; 3d , X = ClO4; LcapL = phen: 3e , X = OTf; 3f , X = ClO4) in which the building blocks LcapL and P(C6H4CH2NMe2‐2)3 act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me2NCH2 built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C6H4CH2NMe2‐2)3 ( 5 ) along with [Ag(phen)2]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P21/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)Å3 and Z = 4 with 8132 observed unique reflections (R1 = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)Å3 and Z = 4 with 6209 observed unique reflections (R1 = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH2C2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion.  相似文献   

16.
The syntheses, characterizations and in vitro cytotoxities of seven soluble silver (I) compounds (1–7) with 2,2′‐bipyridine (bpy), 5,5′‐dimethyl‐2,2′‐bipyridine (dmbpy) and 1, 10‐phenanthroline (phen) are described. Two of the complexes, [Ag(dmbpy)(NO3)] (1) and [Ag(dmbpy)]ClO4(2), have been structurally established by single‐crystal X‐ray diffraction, which reveals the silver(I) atom in compound 1 is in a Y‐shape coordination geometry with two N atoms (av. Ag? N = 227.8 pm) from a chelate dmbpy ligand and an O atom (Ag? O=221.8(4) pm) from a monodentate nitrate. The Ag(I) atom in compound 2 is three‐coordinated by three N atoms, two of which are from a chelate dmbpy, and one from an acetonitrile ligand. The seven compounds showed strong cytotoxities in vitro to both normal and carcinoma cells.  相似文献   

17.
Two novel chiral ruthenium(II) complexes, Δ‐[Ru(bpy)2(dmppd)]2+ and Λ‐[Ru(bpy)2(dmppd)]2+ (dmppd = 10,12‐dimethylpteridino[6,7‐f] [1,10]phenanthroline‐11,13(10H,12H)‐dione, bpy = 2,2′‐bipyridine), were synthesized and characterized by elemental analysis, 1H‐NMR and ES‐MS. The DNA‐binding behaviors of both complexes were studied by UV/VIS absorption titration, competitive binding experiments, viscosity measurements, thermal DNA denaturation, and circular‐dichroism spectra. The results indicate that both chiral complexes bind to calf‐thymus DNA in an intercalative mode, and the Δ enantiomer shows larger DNA affinity than the Λ enantiomer does. Theoretical‐calculation studies for the DNA‐binding behaviors of these complexes were carried out by the density‐functional‐theory method. The mechanism involved in the regulating and controlling of the DNA‐binding abilities of the complexes was further explored by the comparative studies of [Ru(bpy)2(dmppd)]2+ and of its parent complex [Ru(bpy)2(ppd)]2+ (ppd = pteridino[6,7‐f] [1,10]phenanthroline‐11,13 (10H,12H)‐dione).  相似文献   

18.
A binuclear samarium(III) complex with benzoic acid and 1,10‐phenanthroline, [Sm(BA)3phen]2 was synthesized and characterized by elemental analysis, UV, IR and TG‐DTG techniques. The structure of the title complex was established by single crystal X‐ray diffraction. The crystal is triclinic, space group P1 with a = 10.8216(11) Å, b = 11.9129(13) Å, c = 12.425(2) Å, α = 105.007(2)°, β = 93.652(2)°, γ = 113.2630(10)°, Z = 1, Dc = 1.650 mg·m?3, F(000) = 690. The carboxylate groups are bonded to the samarium ion in three modes: bidentate chelating, bidentate bridging, and tridentate chelating‐bridging. Each Sm3+ ion is coordinated to one bidentate chelating carboxylate group, two bidentate bridging and two tridentate chelating‐bridging carboxylate groups, as well as one 1,10‐phenanthroline molecule, forming a nine‐coordinate metal ion. Based on thermal analysis, the thermal decomposition process of [Sm(BA)3phen]2 has been derived.  相似文献   

19.
A complex with eight‐coordinate lead(II ) atom and saccharinate (sac) and 2‐aminomethylpyridine ligands was characterized by IR, elemental analysis and X‐ray crystallography. The lead(II ) complex crystallizes in the monoclinic crystal system with space group P21/c. The single crystal X‐ray analysis shows that the complex is a coordination polymer, [Pb(ampy)(μ‐sac)2]n, in which the lead(II ) ions have a highly distorted bicapped trigonal antiprism coordination. Lead(II ) ions are bridged by carboxyl groups of sac forming one‐dimensional linear chains, running parallel to the a axis. The intrachain Pb···Pb distances are 4.4490(3) and 4.4679(3)Å. The individual chains are connected by N—H···Osulfonyl and Campy—H···Osulfonyl type hydrogen bonds, resulting in a three‐dimensional network. The sac ligand acts as bidentate and bridging ligand, while ampy behaves as an N, N′ donor. The IR spectra of the lead(II ) complex are discussed in detail.  相似文献   

20.
[Pb(phe)2]n ( 1 ) (phe is the abbreviation ofphenylalanine) have been synthesized and characterized by elemental analyses, IR and 1H NMR spectroscopy. The single crystal structure of 1 show the complex to be a 2D chain polymer as a result of phenylalanine bridging. Coordination number of PbII ions is six, PbN2O4, with “stereo‐chemically active” electron lone pairs, and the coordination sphere is hemidirected. To the best of our knowledge, this 2D coordination polymer is the first amino acid lead(II) complex that characterized by X‐ray structural analysis.  相似文献   

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