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1.
The salts - yellow [Cr(NH3)6][Ag(CN)2]3 · 2H2O, red [Co(NH3)6][Ag(CN)2]3 · 2H2O, red [Co(NH3)6][Au(CN)2]3 · 2H2O, pale yellow [Ru(NH3)6][Ag(CN)2]3 · 2H2O, yellow K[Cr(NH3)6]2[Au(CN)2]7 · 4H2O, and colorless [(μ2-NH2)2Pt2(NH3)10][Au(CN)2]6 · 5.5{OS(CH3)2} · 0.5H2O - have been prepared by evaporation of aqueous solutions of potassium dicyanoargenate or potassium dicyanoaurate and salts of the appropriate cations. Hydrogen bonding between the cations and the cyano groups of the anions facilitates the formation of structures with strong metallophilic interactions between the anions. Thus, the [Au(CN)2] or [Ag(CN)2] ions self-associate into linear trimers in the isostructural set of crystals, [Cr(NH3)6][Ag(CN)2]3 · 2H2O (Ag?Ag distance; 3.1610(4) Å), [Co(NH3)6][Ag(CN)2]3 · 2H2O (Ag?Ag distance; 3.1557(2) Å), [Co(NH3)6][Au(CN)2]3 · 2H2O (Au?Au distance; 3.0939(4) Å), and [Ru(NH3)6][Ag(CN)2]3 · 2H2O (Ag?Ag distance; 3.1584(5) Å). Crystalline [(μ2-NH2)2Pt2(NH3)10][Au(CN)2]6 · 5.5{OS(CH3)2} · 0.5H2O also contains nearly linear trimers of the dicyanoaurate ion. Yellow crystals of K[Cr(NH3)6]2[Au(CN)2]7 · 4H2O contain a centrosymmetric, bent chain of seven dicyanoaurate ions with Au?Au separations of 3.1806(3), 3.2584(4), and 3.1294(4) Å.  相似文献   

2.
Ligand-field photolysis of K4[Mo(CN)8] · 2H2O in 98% N2H4 · H2O yields the catalytical decomposition of N2H4 into NH3 and N2. From irradiated solutions of octacyanomolybdate(IV) both in NH3(aq) and 98% N2H4 · H2O(l) as solvents, the salt of the formula (PPh4)2[Mo(CN)4O(NH3)] · 2H2O was isolated. The salt is not formed by direct ligand replacement in tetracyanooxomolybdate(IV) ions derived from K3Na[Mo(CN)4O2] · 6H2O as the solute in similar conditions. The X-ray crystal structure and spectral properties of (PPh4)2[Mo(CN)4O(NH3)] · 2H2O are described. The improved method of the synthesis of K4[Mo(CN)8] · 2H2O is also presented.  相似文献   

3.
Red or orange crystals of [Co(NH3)6]2Cl2[Fe(CN)6] · 4H2O (1), [Co(en)3]2Cl2[Fe(CN)6] · 2H2O (2) and [Co(en)3]4[Fe(CN)6]3 · 21.6H2O (3) were isolated from the aqueous systems Co3+-LN-[Fe(CN)6]4− (LN = NH3, en = 1,2-diaminoethane). In all isolated samples the combination of Mössbauer (δ values were from the range −0.07 to −0.08 mm/s) and IR spectra (ν(CN) stretching vibrations in the range 2015-2047 cm−1) confirms the presence of low spin Fe(II) in [Fe(CN)6]4− anions. X-ray structure analyses corroborate the ionic character of all studied compounds. These contain diamagnetic [Co(NH3)6]3+ (1) or [Co(en)3]3+ (2 and 3) complex cations and diamagnetic [Fe(CN)6]4− complex anions. In compounds 1 and 2 chloride anions are present, too. All three compounds contain water of crystallization, in compound 3 as many as 21.6 molecules per formula unit.  相似文献   

4.
By employing the common precursor Na3[Fe(CN)5(NH3)]·3H2O in a new synthetic approach, the azidopentacyanoferrate(III) ion has been isolated and structurally characterized as (Ph4As)2[Na(H2O)4][Fe(CN)5(N3)] 1. In order to confirm its building block ability, compound 1 has been reacted with the mononuclear complex [Mn(valphen)(H2O)2]ClO4 (H2valphen represents the Schiff base resulting from the condensation of o-vanillin with 1,2-phenylenediamine in a 2:1 M ratio) to afford the new MnIII-FeIII heterometallic system [Mn(valphen)(H2O)2]2[(H2O)(valphen)Mn(μ-CN)Fe(CN)4(N3)]·8H2O 2. The crystal structure of compound 2 reveals a supramolecular assembly generated by [(H2O)(valphen)Mn(μ-CN)Fe(CN)4(N3)]2− dianions and discrete [Mn(valphen)(H2O)2]+ counterions. The dynamic magnetic measurements of compound 2 point to a slow relaxation of the magnetization.  相似文献   

5.
Two new heterometallic complexes, [Cu(en)(H2O)]2[Fe(CN)6]·4H2O (1) and [Cu(en)2][KFe(CN)6] (2), have been isolated from the reactions of CuCl2 and en with K3[Fe(CN)6] in different molar ratios. Both complexes have been characterized by X-ray analyses, IR spectra and elemental analyses. Complex 1 is a cyanide bridged bimetallic assembly, its crystal structure consists of a two-dimensional polymeric sheet with two different rings, one a four-membered square ring and another a 12-membered hexagonal ring. The Fe(II) ion of 1 has two terminal, two linear bridging and two 1,1 en-on bridging cyanide groups. In the crystal structure of 2, the neighboring [Fe(CN)6]3− units are bridged by the K+ and the [K[Fe(CN)6]]2− units forming a three-dimensional network structure. The [Cu(en)2]2+ units fill in the holes of the network acting as counter cations and charge compensations. Variable temperature magnetic susceptibility studies of 1 indicate that the complex exhibits ferromagnetic interaction between the Cu(II) ions.  相似文献   

6.
Two new tetrahedral tungsten cyanide cluster compounds, [Cu(dien)]3[W4Te4(CN)12] · 9H2O (1) (dien=diethylenetriamine) and [Ni(en)(NH3)]3[W4Se4(CN)12] · 7.5H2O (2) (en=ethylenediamine), were synthesized by treating aqueous solutions of the saltlike cluster compound K6[W4Te4(CN)12] · 5H2O/K6[W4Se4(CN)12] · 6H2O with copper(II)/nickel(II) chloride in aqueous ammonia containing dien/en. The cyano-bridged layered coordination polymeric compounds were characterized by single-crystal X-ray diffraction analysis: monoclinic, space group P21 for 1; trigonal, space group for 2. Structures of 1 and 2 consist of infinite neutral layers of cluster components {W4Te4(CN)12}/{W4Se4(CN)12} connected, one another by {Cu(dien)} or {Ni(en)(NH3)} fragments, respectively.  相似文献   

7.
The octanuclear cyano-bridged cluster [(Tp)8Fe4Ni4(CN)12] · H2O · 24CH3CN (1) (Tp = hydrotris(1-pyrazolyl)borate) showing magnetic properties of single-molecule magnet has been synthesized by reaction of [fac-Fe(Tp)(CN)3] with {(Tp)Ni(NO3)} species formed from an equimolar reaction mixture of Ni(NO3)2 · 6H2O and KTp in MeCN. The X-ray analysis of 1 shows molecular cube structure in which FeIII and NiII ions reside in alternate corners. The average intramolecular Fe?Ni distance is 5.124 Å. Out-of-phase ac susceptibility and reduce magnetization measurements show that 1 is a single molecule magnet with ground spin state S = 6 and spin reversal energy barrier U = 14 K. Magnetic hysteresis loops were also observed by applying fast sweeping field.  相似文献   

8.
The reaction of FeCl3 · 6H2O, potassium hydrotris(pyrazolyl)borate (KTp) and KSCN gives [FeTp2][TpFe(NCS)3] (1) and [FeTp2]3[Fe(NCS)6] (2), respectively. The bond lengths and angles indicate that both complexes have [FeTp2]+ cations where Fe(III) ions are in typical low-spin state, and in counter ions, [TpFe(NCS)3] for 1 and [Fe(NCS)6]3− for 2 are both in high-spin state. Variable temperature magnetic susceptibility and ESR results also show that there are double spin states of iron(III) ions within the crystal lattice of both compounds.  相似文献   

9.
By reaction of Zn4O(O2CNMe2)6 (1) with [NH2Me2][O2CNMe2] in toluene as medium, the homoleptic zinc compound [Zn(O2CNMe2)2] (2) was obtained, which reverted back to the tetranuclear μ-oxo derivative by controlled hydrolysis. The reaction of ZnO in MeCN with an excess of [NH2Me2][O2CNMe2] in concentrated solution produced high yields of [Zn(O2CNMe2)2] (2) or [NH2Me2][Zn2(O2CNMe2)5] · xMeCN, 3 · xMeCN, x = 1 or 2, depending on the experimental conditions.  相似文献   

10.
A new family of mononuclear Zn(II) complexes [Zn(Pyimpy)2](ClO4)2 (1), [Zn(Pyimpy)(Cl)2] (2), [Zn(Pyimpy)(SCN)2] (3) and [Zn(Pyimpy)(N3)2] (4) were synthesized using designed tridentate ligand Pyimpy having NNN donors (Pyimpy: (2-((2-phenyl-2-(pyridin-2-l)hydazono)methyl)pyridine)). Complexes were characterized by different spectroscopic studies and it has been found out that all complexes exhibited strong fluorescent emission at room temperature. Molecular structures of [Zn(Pyimpy)2](ClO4)2·C6H5CH3·0.5H2O (1·C6H5CH3·0.5H2O) and [Zn(Pyimpy)(Cl)2]·CH3CN (2·CH3CN) were determined by X-ray crystallography and ligand coordinated Zn(II) ions was described as distorted octahedral and distorted square pyramidal, respectively. DNA binding properties of these complexes were investigated by absorption spectral, fluorescence quenching and circular dichroism spectral studies.  相似文献   

11.
Double complex salts [M(NH3)4][M′(Ox)2(H2O)2] · 2H2O (M = Pd, Pt, M′ = Ni, Zn) were synthesized by combination of solutions containing corresponding cations [M(NH3)4]2+ and anions [M′(Ox)2(H2O)2]2−. The salts obtained were characterized by IR spectroscopy, thermal analysis, powder and single crystal X-ray diffraction. The prepared compounds are isostructural and crystallize in the orthorhombic crystal system (space group I222, Z = 2). Thermal decomposition of the salts in helium or hydrogen atmosphere at 200-400 °C results in formation of nano-sized bimetallic powders. Depending on the phase diagram of the respective bimetallic system and temperature conditions, they can be single phase or multiphase products. In particular, thermal decomposition of double complex salts [M(NH3)4][Zn(Ox)2(H2O)2] · 2H2O (M = Pd, Pt) results in formation of PdZn and PtZn intermetallic compounds, correspondingly. Decomposition of [Pd(NH3)4][Ni(Ox)2(H2O)2] · 2H2O affords a disordered solid solution Pd0.5Ni0.5. Disordered Pt0.5Ni0.5 was obtained from [Pt(NH3)4][Ni(Ox)2(H2O)2] · 2H2O in helium atmosphere, while in hydrogen atmosphere - a two-phase mixture of disordered Pt0.5Ni0.5 and ordered PtNi. In all cases crystallite sizes of bimetallic particles varied within 50-250 Å.  相似文献   

12.
Two new zinc-triazole-carboxylate frameworks constructed from secondary building units (SBUs), [Zn5(trz)4(btc)2(DMF)2(H2O)2]·2H2O·DMF (1) and [Zn4(trz)3(btc)2(CH3CN)(H2O)]·5H2O·(Bu4N) (2), [Htrz = 1,2,4-triazole, H3btc = 1,2,4-benzenetricarboxylate, Bu4N = tetrabutylammonium], have been synthesized by solvothermal reactions and characterized by single-crystal X-ray diffraction analyses, X-ray power diffraction, elemental analyses, infrared spectra and thermogravimetric analyses. Both compounds 1 and 2 exhibit 3D (3,8)-connected tfz-d nets with {43}2{46.618.84} topology symbol built from rod-shaped {[Zn5(trz)4]6+}n SBUs (1) and {[Zn4(trz)3]5+}n SBUs (2). In two compounds, rodlike units are connected by btc ligands via different modes. Additionally, solid state fluorescent emission spectra of two compounds show fluorescent properties at room temperature.  相似文献   

13.
Crystallisation of simple cyanoruthenate complex anions [Ru(NN)(CN)4]2− (NN = 2,2′-bipyridine or 1,10-phenanthroline) in the presence of Lewis-acidic cations such as Ln(III) or guanidinium cations results, in addition to the expected [Ru(NN)(CN)4]2− salts, in the formation of small amounts of salts of the dinuclear species [Ru2(NN)2(CN)7]3−. These cyanide-bridged anions have arisen from the combination of two monomer units [Ru(NN)(CN)4]2− following the loss of one cyanide, presumably as HCN. The crystal structures of [Nd(H2O)5.5][Ru2(bipy)2(CN)7] · 11H2O and [Pr(H2O)6][Ru2(phen)2(CN)7] · 9H2O show that the cyanoruthenate anions form Ru-CN-Ln bridges to the Ln(III) cations, resulting in infinite coordination polymers consisting of fused Ru2Ln2(μ-CN)4 squares and Ru4Ln2(μ-CN)6 hexagons, which alternate to form a one-dimensional chain. In [CH6N3]3[Ru2(bipy)2(CN)7] · 2H2O in contrast the discrete complex anions are involved in an extensive network of hydrogen-bonding involving terminal cyanide ligands, water molecules, and guanidinium cations. In the [Ru2(NN)2(CN)7]3− anions themselves the two NN ligands are approximately eclipsed, lying on the same side of the central Ru-CN-Ru axis, such that their peripheries are in close contact. Consequently, when NN = 4,4′-tBu2-2,2′-bipyridine the steric bulk of the t-butyl groups prevents the formation of the dinuclear anions, and the only product is the simple salt of the monomer, [CH6N3]2[Ru(tBu2bipy)(CN)4] · 2H2O. We demonstrated by electrospray mass spectrometry that the dinuclear by-product [Ru2(phen)2(CN)7]3− could be formed in significant amounts during the synthesis of monomeric [Ru(phen)(CN)4]2− if the reaction time was too long or the medium too acidic. In the solid state the luminescence properties of [Ru2(bipy)2(CN)7]3− (as its guanidinium salt) are comparable to those of monomeric [Ru(bipy)(CN)4]2−, with a 3MLCT emission at 581 nm.  相似文献   

14.
The self assembly of [FeIII(L)]Cl2ClO4 (L = pentadentate macrocyclic ligand) with octacyano metallates [MIV(CN)8]4− (M = Mo, W) leads to bimetallic cyano-bridged 2-D coordination polymers of formula [{Fe(L)}3{M(CN)8}2]Cl·xH2O with M = Mo (2), or W (3). The structure of the tungsten analogue has been established by single crystal X-ray diffraction. The magnetic properties for both Mo and W derivative are reported.  相似文献   

15.
The reaction of xanthosine-5′'-monophosphate disodium salt (5′-XMPNa2) with Pt(II), Cu(II) and Mg(II) ions produced compounds of the type cis- and trans-Pt(NH3)2(XMPNa2)nCl2·xH2O, where n = 1 or 2; Pt(XMPNa2)nCl2·xH2O, where n = 1-4, x = 1,4 & 6; Cu(XMP)·6H2O and Mg(XMP)·xH2O, where x = 9 or 4. In the complexes synthesized here at neutral pH values, the nucleotide binds through the N7-atom of the purine ring system, whereas for Cu(II) and Mg(II) compounds obtained at pH = 4 a direct metal-phosphate interaction as well as Nτ bonding is proposed.  相似文献   

16.
A new mononuclear tetracyanometallic complex, (n-Bu4N)[(dbphen)Fe(CN)4] (1, dbphen = 5,6-dibromo-1,10-phenanthroline), has been prepared by reacting [(dbphen)FeII(py)2(SCN)2] and KCN in water and further oxidized with chlorine. With the use of 1 as building block, two trinuclear Fe2M complexes, [(dbphen)2Fe2(CN)8Cu(Me3tacn)]·3H2O (2), [(dbphen)2Fe2(CN)8Ni(dabhctd)]·2H2O (3) and a chain complex of squares [(dbphen)2Fe2(CN)8Co(MeOH)2]n (4), have been synthesized and structurally characterized. Magnetic studies show ferromagnetic coupling between FeIII and MII (M = Cu, 2; Ni, 3) ions bridged by cyanides in complexes 2 and 3, while complex 4 exhibits meta-magnetic behavior.  相似文献   

17.
Two new zinc phosphonates with 2-hydroxyphosphonoacetic acid (HPAA) and 1-hydroxyethylidenediphosphonic acid (hedpH4), [Zn2{HO3PCH(OH)CO2}3]·2NH2(CH3)2·3H2O (1) and [Zn3{CH3C(OH)(PO3)2}2]·2NH2(CH3)2·H2O (2) have been synthesized under mixed-solvothermal conditions at 160 °C and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy and elemental analysis. The structure of compound 1 comprises Zn1O6 and Zn2O6 octahedra connected by [HO3PCH(OH)CO2]2− to form a 2D layered structure with one-dimensional channel system along c-axis direction, and the protonated dimethylamine cations are being located between two adjacent layers. Interestingly the layers of 1 arranged in an alternative sequence (ABAB). Compound 2 features a 3D framework structure with channels along the b- and c-axis, respectively. The charge-compensating protonated Hdma+ cations and solvate water molecules are located inside the channels along the c-axis. A notable feature for compound 2 is the presence of the alternate left- and right-handed helical chains in the structure. The luminescence properties of compounds 1 and 2 have also been studied.  相似文献   

18.
By applying the hydrothermal in situ acylation reactions between alkyl-substituted pyridine-2,3-dicarboxylic acids and hydrazine hydrate, six pyridine-monoacylhydrazidate-coordinated transition-metal complexes [Mn(MPDH)2] 1, [M(MPDH)2(H2O)2]·2H2O (M2+ = Co2+2, Zn2+3), [Mn(EPDH)2(H2O)2] 4 and [M(EPDH)2(H2O)2] (M2+ = Zn2+5, Co2+6) (MPDH = 6-methylpyridine-2,3-dicarboxylhydrazidate; EPDH = 5-ethylpyridine-2,3-dicarboxylhydrazidate) were obtained. Although only compound 1 is a 1-D chained coordination polymer and the others are the mononuclear molecular entities, they all further self-assemble into the interesting supramolecular networks via hydrogen-bonded interactions between pyridine-monoacylhydrazidate ligands. Two Zn2+ compounds 3 and 5 possess the fluorescence properties with maximum emissions at 517 nm for 3 and 530 nm for 5 upon excitation, respectively. The magnetic analysis for compound 1 indicates there exists the antiferromagnetic interactions between the Mn(II) ions.  相似文献   

19.
Reaction of [Ru2(O2CMe)4]Cl with K3[Cr(CN)5NO] in water forms Hx[RuII/III2(O2CMe)4]3−x-[Cr(CN)5NO]·zH2O (x = 0.2) that magnetically orders at 4.0 K and possesses an interpenetrating body centered cubic [a = 13.2509(2) Å] structure with random locations of the bridging nitrosyl ligands, and x/3 vacant cation sites. Similarly, the aqueous reaction of [Ru2(O2CMe)4]Cl with Na2[Fe(CN)5NO] forms paramagnetic [Ru2(O2CMe)4]2[Fe(CN)5NO]·H2O, which has a similar tetragonal interpenetrating structure [a = 13.0186(1) Å, c = 13.0699(2) Å] where the NO ligands are presumably nonbridging and 1/3 of the expected cation sites are unoccupied. The presence of uncoordinated NO sites in addition to missing neighboring [Ru2(O2CMe)4]+ units, results in significant vacancies (or holes) in the lattice.  相似文献   

20.
The reaction of Zn(ClO4)2 · 6H2O and Cu(ClO4)2 · 6H2O with H3Sas (H3Sas = N-(2-hydroxybenzyl)-L-aspartic acid in water afforded the complexes [Zn6(Sas)4(H2O)8]·5H2O (1) and [Cu(HSas)(H2O)] (2), respectively, which were characterized by infrared spectroscopy, elemental analysis, thermogravimetry and single-crystal X-ray crystallography. In 1, the pentanuclear clusters formed by four H3Sas ligands and five Zn(II) metal ions are bridged by the “[Zn(H2O)4]2+” cations to form 1D polymeric chains. While in 2, the mononuclear [Cu(HSas)(H2O)] repeating units form a 1D zigzag chain and further extended by strong intermolecular hydrogen bonds to form a 2D sheet. The different coordination geometries of Cu(II) and Zn(II) show significant influence on the polymeric structures.  相似文献   

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