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1.
The synthesis and crystal structure elucidation of a novel dinuclear heteroleptic copper(II) complex has led to an alternative mechanism in the formation of covalent hydrates. During further studies on the synthesis and properties of [Cu2(ophen)2] ( 1 ), a dinuclear complex of copper(I) with 1 H‐[1,10]‐phenanthrolin‐2‐one (Hophen), two intermediates/alternative products 2 and 3 were isolated. The dinuclear, antiferromagnetic complex [Cu2(ophen)2(phen)2] ? (NO3)2 ? 9H2O ( 3 , phen=1,10‐phenanthroline) contains two five‐coordinate copper(II) ions, both with trigonal‐bipyramidal coordination, which are bridged together through deprotonated hydroxyl groups with a Cu? Cu non‐bonding distance of 3.100 Å. Complex [Cu(phen)2(H2O)] ? (NO3)2 ( 2 ) is a polymorph of a previously reported material. The occurrence of 2 and 3 has led us to propose a variation to the Gillard mechanism for the formation of covalent hydrates in bidentate N‐heterocycles in which the attacking nucleophile may be the deprotonated form of 2 , [Cu(phen)2(OH)]?, rather than free OH?.  相似文献   

2.
Two cyano‐bridged polymers, [Cu3(CN)3(phen)]n ( 1 ) and [Cu(CN)(phen)]n ( 2 ) (phen = 1,10‐phenphralonine), were synthesized by the hydrothermal reaction of Cu(NO3)2· 3H2O, K3[Fe(CN)6] and phen and were characterized structurally by X‐ray, IR and ERSC methods. Compound 1 shows a two‐dimensional folded coordination network by Cu(I)? CN? Cu(I) and Cu(I)? Cu(I) interaction, while compound 2 exhibits an infinite helix chain by Cu(I)? CN linkages. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

3.
Two new CoII 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 CoII ions in 1 .  相似文献   

4.
Two cobalt phosphonates, [Co2(2,2′‐bpy)2(H2O)(pbtcH)] ( 1 ) and [Co2(H2O)(pbtcH)(phen)2] ( 2 ; pbtcH5=5‐phosphonatophenyl‐1,2,4‐tricarboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), with layer structures are reported. Compound 1 contains O‐C‐O and O‐P‐O bridged tetramers of Co4, which are further connected by pbtcH4? units to form a layer. In compound 2 , the cobalt tetramers made up of water‐bridged Co2 dimers and O‐P‐O linkages are connected into a layer by pbtcH4? units. Upon dehydration, compounds 1 and 2 experience single‐crystal‐to‐single‐crystal (SC–SC) structural transformations to form [Co2(2,2′‐bpy)2(pbtcH)] ( 1 a ) and [Co2(pbtcH)(phen)2] ( 2 a ), respectively. The process is reversible in each case. Notably, a breathing effect is observed for 1 , accompanied by pore opening and closing due to the reorientation of the coordinated 2,2′‐bpy molecules. The transformation was also monitored by in situ IR measurements. Magnetic studies reveal that antiferromagnetic interactions are mediated between the magnetic centers in compounds 1 and 1 a , whereas ferromagnetic interactions are dominant in compound 2 .  相似文献   

5.
Two new coordination polymers [Co2(pbc)4(H2O)]n ( 1 ) and [Mn(pbc)2] ( 2 ) (Hpbc = 4‐pyrid‐3‐ylbenzoic acid) were obtained by hydrothermal reaction and characterized by elemental analysis, IR spectroscopy, and single‐crystal X‐ray diffraction. Compound 1 features a 3D network with a four‐connected 66 net constructed from secondary building units of dinuclear cobalt. Compound 2 exhibits a six‐connected 412 · 63 topology based on dinuclear manganese.  相似文献   

6.
The α‐[P2W18O62]6–‐based coordination polymer [Cu2(phen)3(H2O)3(P2W18O62)][Cu(phen)2(H2O)] · 5H2O ( 1 ) (phen = phenanthroline), was hydrothermally synthesized and characterized by single‐crystal and powder X‐ray diffraction, IR and UV/Vis diffuse reflection spectroscopy, and elemental analysis. Structural studies reveal that compound 1 exhibits a three‐dimensional (3D) supramolecular structure based on π–π and hydrogen bonding interactions. In addition, visible light driven photocatalytic experiments of compound 1 were also studied.  相似文献   

7.
Three new compounds based on H2BDC and PyBImE [H2BDC = 1,4‐benzenedicarboxylatic acid, PyBImE = 2‐(2‐pyridin‐4‐yl‐vinyl)benzimidazole], namely, [Co(PyBImE)(BDC)(H2O)2] ( 1 ), [Co(PyBImE)2(HBDC)(BDC)0.5] ( 2 ), and [(HPyBImE)+ · (BDC)20.5 · (H2BDC)0.5] ( 3 ), were synthesized by hydrothermal methods and characterized by single‐crystal X‐ray diffraction. Compound 1 is a one‐dimensional chain bridged by terephthalate in a bis(monodentate) fashion. In the complex the nitrogen atom from NBIm and the coordination water molecule complete the coordination sphere. In complex 2 , the dinuclear cobalt units are bridged by terephthalate in a bis(bidentate) fashion into a one‐dimensional chain, but different from complex 1 , the nitrogen atom from NPy and the oxygen atom from hydrogenterephthalate complete the coordination sphere. Complex 3 is a co‐crystal with PyBImE and H2BDC in a 1:1 ratio and the transfer of hydrogen atoms leads the complex into a salt. Interesting supramolecular structures are shown due to the hydrogen bonding as well as π ··· π interactions in the three complexes. Thermal and magnetic properties of 1 and 2 were also studied.  相似文献   

8.
The dicyanamide‐bridged polymers with Schiff‐base ligand, [CoNaL(dca)]n ( 1 ) and [Mn2L(dca)2]n ( 2 ) [H2L = bis(3‐methoxysalicylidene)benzene‐1,2‐diamine, dca = dicyanamide] were synthesized and characterized by elemental analyses, IR spectrroscopy and single‐crystal X‐ray diffraction. The solid‐state structures reveal that polymer 1 has double dca bridged loop‐like 1D chains, in which the heterodinuclear Co2+‐Na+ units (LCoNa) are bridged by dca with coordination mode μ1,3,5. In polymer 2 , homodinuclear Mn2+‐Mn2+(LMnMn) units are linked by dca in μ1,5‐bridging mode to form 2D planes. Magnetic susceptibility studies on 2 reveals antiferromagnetic coupling interactions between the adjacent Mn2+ ions in the LMnMn unit.  相似文献   

9.
The novel PtII–dibenzo‐18‐crown‐6 (DB18C6) title complex, μ‐[tetrakis­(thio­cyanato‐S)­platinum(II)]‐N:N′‐bis{[2,5,8,­15,18,21‐hexa­oxa­tri­cyclo­[20.4.0.19,14]­hexa­cosa‐1(22),9(14),10,12,23,25‐hexaene‐κ6O]­potassium(I)}, [K(C20H24O6)]2[Pt(SCN)4], has been isolated and characterized by X‐ray diffraction analysis. The structure analysis shows that the complex displays a quasi‐one‐dimensional infinite chain of two [K(DB18C6)]+ complex cations and a [Pt(SCN)4]2? anion, bridged by K+?π interactions between adjacent [K(DB18C6)]+ units.  相似文献   

10.
A three‐dimensional cyano‐bridged copper(II) complex, [Cu(dien)Ag(CN)2]2[Ag2(CN)3][Ag(CN)2] ( 1 ) (dien = diethylenetriamine), has been prepared and characterized by X‐ray crystallography. Complex 1 crystallized in the monoclinic space group P21/n with a = 6.988(2), b = 17.615(6), c = 12.564(4) Å, β = 90.790(5)°. The crystal consists of cis‐[Cu(dien)]2+ units bridged by [Ag(CN)2] to form a zig‐zag chain. The Ag atoms of the free and bridging [Ag(CN)2] link together to form additional infinite zig‐zag chains with short Ag···Ag distances. The presence of Ag···Ag interactions effectively increases the dimensionality from a 1‐D chain to a 3‐D coordination polymer.  相似文献   

11.
Two copper‐containing compounds based on MoO42–, [Cu4(phen)42‐OH)23‐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 MoO42– by hydrogen bonds in 1 at low temperature and 2D layer water clusters are formed by (H2O)16 units in 2 .  相似文献   

12.
Reactions of copper(I) halides (Cl, Br, I) with 1‐methyl‐1, 3‐imidazoline‐2‐thione (mimzSH) in 1 : 2 molar ratio yielded sulfur‐bridged dinuclear [Cu2X2(μ‐S‐mimzSH)21‐S‐mimzSH)2] (X = I, 1 , Br, 2 ; Cl, 3 ) complexes. Copper(I) iodide with 1,3‐imidazoline‐2‐thione (imzSH2) and Ph3P in 1 : 1 : 1 molar ratio has also formed a sulfur‐bridged dinuclear [Cu2I2(μ‐S‐imzSH2)2(PPh3)2] ( 4 ) complex. The central Cu(μ‐S)2Cu cores form parallelograms with unequal Cu–S bond distances {2.324(2), 2.454(3) Å} ( 1 ); {2.3118(6), 2.5098(6) Å} ( 2 ); {2.3075(4), 2.5218(4) Å} ( 3 ); {2.3711(8), 2.4473(8) Å} ( 4 ). The Cu···Cu separations, 2.759–2.877Å in complexes 1 – 3 are much shorter than 3.3446Å in complex 4 . The weak intermolecular interactions {H2CH···S# ( 2 ); CH···Cl# ( 3 ); NH···I# ( 4 )} between dimeric units in complexes 2 – 4 lead to the formation of linear 1D polymers.  相似文献   

13.
The cyano‐bridged heteronuclear coordination polymer poly[tris[(5,12‐dimethyl‐7,14‐diphenyl‐1,4,8,11‐tetraazacyclo­tetra­deca‐4,11‐diene)copper(II)]‐hexa‐μ‐cyano‐bis[tricyano­cobalt(III)] di­methyl­formamide solvate trihydrate], {[Cu3Co2(CN)12(C24H32N4)3]·C3H7NO·3H2O}n, was synthesized by the assembly reaction of [CuL]2+ (L is 5,12‐dimethyl‐7,14‐di­phenyl‐1,4,8,11‐tetraazacyclotetradeca‐4,11‐diene) and [Co(CN)6]3− in a dimethyl­formamide–water solution. The structure consists of neutral cyano‐bridged Cu3Co2 units with the unique Co atom in a general position and all three Cu atoms on independent inversion centres. Each [Co(CN)6]3− ion connects three CuII ions via three cyano groups to form a novel cyano‐bridged two‐dimensional stair‐shaped‐layer structure. The water and dimethyl­formamide molecules are situated in the inter‐fragment spaces.  相似文献   

14.
The salts [Cu(phen)3][Cu(pheida)2]·10H2O ( 1 ) and [(phen)2Cu(μ‐BAAP)Cu(μ‐BAAP)Cu(phen)2][Cu(BAAP)2]·8.5H2O ( 2 ) (H2pheida = N‐phenetyl‐iminodiacetic acid, H2BAAP = N‐benzylaminoacetic‐2‐propionic acid, phen = 1, 10‐phenanthroline) have been prepared and studied by thermal, spectroscopic and X‐ray diffraction methods. 1 has the rather unusual [Cu(phen)3]2+ cation and two non‐equivalent [Cu(pheida)2]2— anions with a coordination type 4+2 but quite different tetragonality (T = 0.848 and 0.703 for anions 1 and 2, respectively). The crystal consists of multi‐π, π‐stacked chains (…anion 2 — cation — cation — anion 2…) connected by hydrophobic interactions; these chains build channels which are partially filled by anions 1 and water molecules. In contrast, compound 2 has a mixed‐ligand trinuclear cation with a bridging central moiety close similar to the counter anion. The formation of such a trinuclear cation is discussed as a consequence of the most advantageous molecular recognition process between [Cu(phen)2(H2O)1 or 2]2+ and [Cu(BAAP)2]2— in solution. In the crystal of 2, multi‐π, π‐stacked arrays of C6‐rings from phen and (BAAP)2— ligands of trinuclear cations generate channels where counter anions and water molecules are located.  相似文献   

15.
Three new Keggin polyoxometalate (POM)-based compounds linked to 3d metal complexes have been synthesized under hydrothermal conditions: [Cu(phen)2]2{[Cu(phen)]2 [SiMo12O40(VO)2]} (1), {[Zn(phen)2]2[GeMo12O40(VO)2]}{[Zn(phen)2(H2O)]2 [GeMo12O40(VO)2]}·3H2O (2) and {[Co(phen)2]2[PMo12O40(VO)2]}{[Co(phen)2(OH)]2 [PMo12O40(VO)2]}·2.5H2O (3) (phen=1,10-phenanthroline). These three compounds present, as building blocks, the bicapped Keggin anions [XMo12O40(VO)2] (X=Si, Ge and P). Compound 1 consists of a bicapped Keggin anion [SiMo12O40(VO)2]2− linked to two [Cu(phen)]+ complexes with two [Cu(phen)2]+ countercations. Compound 2 contains two bicapped Keggin anions [GeMo12O40(VO)2]4−, one linked to two [Zn(phen)2(H2O)]2+ cations and the other one linked to two [Zn(phen)2]2+ cations. Compound 3 is a two-dimensional POM-based square network formed by bicapped Keggin anions [PMo12O40(VO)2]4− connected by [Co(phen)2]2+ cations. Discrete bicapped Keggin anions [PMo12O40(VO)2] linked to two [Co(phen)2(OH)]+ cations are located between the layers. The magnetic properties show the presence of antiferromagnetic interactions among the reduced Mo(V) atoms (in the three compounds) plus a paramagnetic contribution from the V(IV) atoms (in 1 and 2). Compound 3 shows, in addition, an antiferromagnetic interaction between the Co(II) and the V(IV) ions directly linked through an oxygen bridge. The low-temperature ESR spectra of compound 3 confirm the presence of the reduced Mo(V) ions and the antiferromagnetic coupling between the Co(II) and the V(IV) ions.  相似文献   

16.
Two new molybdenum phosphate complexes, [Cu2(phen)4(μ‐Cl)][PMo12O40]·H2O (phen = 1,10‐phenanthroline) ( 1 ) and (Hbpy)[CuI(bpy)]2[PMoV2MoVI10O39] (bpy = 4,4′‐bipyridine) ( 2 ), have been prepared under mild hydrothermal conditions and structurally characterized by single‐crystal X‐ray diffraction. Compounds 1 and 2 crystallize in triclinic system, space group , with a = 12.5458(7) Å, b = 13.4486(8) Å, c = 21.2406(12) Å, α = 99.7020(10)°, β = 94.2320(10)°, γ = 95.0890(10)°, V = 3504.2(3) Å3 and Z = 2 for 1 , and a = 10.7871(6) Å, b = 10.9016(6) Å, c = 12.7897(7) Å, α = 96.8500(10)°, β = 110.0850(10)°, γ = 103.5800(10)°, V = 1339.74(13) Å3 and Z = 1 for 2 . Compound 1 contains a [Cu2(phen)4(μ‐Cl)]3+ cation in which two similar [Cu(phen)2] units are bridged by one chlorine atom. Compound 2 contains one‐dimensional straight chain of Keggin polyoxoanions [PMoV2MoVI10O39]n3? and two linear cationic chains of [CuI(bpy)]nn+. The molecular packing shows a two‐dimensional network, which is formed by the cross of the linear Keggin anions and Cu‐bpy cations.  相似文献   

17.
Three coordination compounds [Mn3(dmb)6(H2O)4(4, 4′‐bpy)3(EtOH)]n ( 1 ) and [M(dmb)2(pyz)2 (H2O)2] [MII = Co ( 2 ), Mn ( 3 )] (Hdmb = 2, 6‐dimethoxybenzoic acid, 4, 4′‐bpy = 4, 4′‐bipyridine, pyz = pyrazine) were synthesized and characterized by single‐crystal X‐ray diffraction analysis. Compound 1 consists of infinite 1D polymeric chains, in which the metal entities are bridged by 4, 4′‐bpy ligands. There are four crystallographically independent MnII atoms in the linear chain with different coordination modes, which is only scarcely reported for linear polymers. The isostructural crystals of 2 and 3 are composed of neutral mononuclear complexes. In crystal the complexes are combined into chains by intermolecular O–H ··· N hydrogen bonds and π–π interactions between antiparallel pyrazine molecules.  相似文献   

18.
The proton‐induced Ru?C bond variation, which was previously found to be relevant in the water oxidation, has been investigated by using cyclometalated ruthenium complexes with three phenanthroline (phen) isomers. The designed complexes, [Ru(bpy)2(1,5‐phen)]+ ([ 2 ]+), [Ru(bpy)2(1,6‐phen)]+ ([ 3 ]+), and [Ru(bpy)2(1,7‐phen)]+ ([ 4 ]+) were newly synthesized and their structural and electronic properties were analyzed by various spectroscopy and theoretical protocols. Protonation of [ 4 ]+ triggered profound electronic structural change to form remote N‐heterocyclic carbene (rNHC), whereas protonation of [ 2 ]+ and [ 3 ]+ did not affect their structures. It was found that changes in the electronic structure of phen beyond classical resonance forms control the rNHC behavior. The present study provides new insights into the ligand design of related ruthenium catalysts.  相似文献   

19.
The title compound, [Cu2(C2H3O2)4(C11H9N)2] or [Cu2(MeCO2)4(phpy)2] (phpy is 4‐phenyl­pyridine), consists of centrosymmetric dimers in which the CuII atoms display a square‐pyramidal CuO4N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions.  相似文献   

20.
Slow diffusion reaction of 2,2′‐dithiodibenzoic acid (dtdb) with CuCl2 in the presence of N‐donor ligands results in the formation of different coordination polymers where both S–S and C–S scission and oxidation of S is observed. X‐ray diffraction analysis of [Cu(tdb)(phen)(H2O)]2 · 2H2O.2DMF] ( 1 ), [Cu(tdb)(py)2(H2O)]2 ( 3 ), and [Cu(tdb)(bipy)(H2O)]2 · 0.5H2O ( 4 ) (tdb = thiodibenzoic acid, phen = phenanthroline, py = pyridine, bipy = 2,2′‐bipyridine) show that the metal ions are coordinated to the carboxylate oxygen atoms of the in situ generated tdb ligand in a monodenate fashion. In [Cu(phen)(SO4)2(H2O)2]n ( 2 ) and [Cu(bipy)(SO4)2(H2O)2]n ( 5 ), the sulfur is oxidized to sulfate ions prior to coordination with the metal. Complex 1 has a dimeric structure with π–π interactions between the phen ligands, whereas 3 and 4 form 1D polymeric chains.  相似文献   

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