Polymeric Cadmium Research Articles

Synthesis, Crystal Structure, and Fluorescence Property of a Thiocyanato-Bridged Polymeric Cadmium(II) Complex Derived from (1-Pyridin-2-ylethylidene)pyridin-2-ylmethylamine

Synthesis, Crystal Structure, and Fluorescence Property of a Thiocyanato-Bridged Polymeric Cadmium(II) Complex Derived from (1-Pyridin-2-ylethylidene)pyridin-2-ylmethylamine

Coordination polymers of sodium 2-(quinolin-8-yloxy)propionate: A receptor for selective metal ions

Unusual bifurcated and trifurcated carboxylate binding to sodium ions in a one dimensional coordination polymer, [{Na2L(H2O)3}Br·H2O]n (1) (where L=2-(quinolin-8-yloxy)propionate), was observed. The ionic coordination polymer 1, possessing bromide anions, has sodium ions in two independent coordination environments. Reaction of 1 with perchloric acid led to anion exchange to form the dinuclear complex [Na2(HL)2(ClO4)2(μ-H2O)] (2). A cadmium coordination polymer [Cd(L)Br]n (3) was prepared by reacting 1 with cadmium(II) acetate. This one dimensional cadmium coordination polymer 3 has cadmium ions in a distorted square pyramidal geometry. The uniqueness of the cadmium polymer is that the bromide ions are inside the coordination sphere and it forms parallel sheet-like structures of polymeric chains through bromide–bromide interactions. The coordination polymer 1 and the dinuclear complex 2 are weakly fluorescent, whereas complex 3 is highly fluorescent. The coordination polymers 1 and 2 are fluorescence receptors for Mg, Ca, Ba, Zn, Cd and Hg in the (+2) oxidation state.

Use of a chitosan–cadmium polymer as a redox hybridization indicator for CaMV35S promoter gene detection

A water-soluble chitosan-coordinated cadmium polymer was synthesized, and its recognition of single-stranded and double-stranded DNA was investigated. The electrochemical analysis in the homogeneous solutions revealed that the chitosan-coordinated cadmium polymer association with a single stranded DNA was 48 times greater than with double-stranded DNA due to the different interaction with the two kinds of DNA. The surface-based electrochemically absorbed chitosan-coordinated cadmium polymer molecules were easily removed from the double-stranded DNA-modified electrode via rinsing but could not be removed from a single-stranded DNA-modified electrode. Based on this fact, the polymer was utilized as a redox indicator for DNA hybridization detection, as the polymer was able to recognize complementary, noncomplementary, and base-mismatched sequences with a low background interference. The target DNA sequence was quantified from 5.0 × 10-9 to 5.0 × 10-7 M with a detection limit of 4.2 × 10-9 M. The polymerase chain reaction amplification of DNA from the real sample of a kind of transgenically modified soybeans was also detected satisfactorily.

Di-, tri-, tetranuclear clusters and polymeric cadmium compounds: Syntheses, structures and fluorescent properties with various linking fashions and high stability of orotates under the condition of strong bases

Assembly reactions of orotic acid (H 3dtpc ) and CdCl 2·2.5H 2O or CdSO 4·8H 2O yielded four new cadmium compounds {[Cd(H 2dtpc)(phen)(H 2O) 2]·(H 2dtpc)·4H 2O} 2 ( 1: solution reaction, pH=4–5, in addition of phen), [Cd 3(dtpc) 2(phen) 5]·13H 2O ( 2: hydrothermal reaction, initial pH=14, final pH=7.5), [Cd(Hdtpc)(H 2O) 3] 4 ( 3: solution reaction, initial pH=6.5, final pH=6.0), {[Cd(Hdtpc)(phen)(H 2O)]·H 2O} n ( 4: hydrothermal reaction, initial pH=8; final pH=6.5), respectively. Compounds 1– 4 have been characterized by IR, thermogravimetric analyses (TGA), photoluminescence analyses, single-crystal and powder X-ray diffraction (PXRD). Compound 1 is a binuclear, 2 is a trinuclear, 3 is a tetranuclear structure, and 4 possesses one-dimensional chain framework, respectively, in which the orotate ligands show seven different linking fashions in 1– 4. The orotate ligands as trivalence anions are observed in the formation of orotate-compounds, in which the orotates show high stability under the extreme condition of strong basic solution, high temperature and pressure.

Rational Construction of Polymeric Cadmium(II) Benzimidazole for Transition Metal Ion Exchange

AbstractA 1D double‐helical coordination polymer {[Cd(pbbm)2]2(ClO4)4(H2O)2}n (1) was successfully constructed by the reaction of Cd(ClO4)2·6H2O with 1,1′‐(1,5‐pentanediyl)bis‐1H‐benzimidazole (pbbm). Interestingly, polymer 1 exhibits highly selective capacity for the ionic exchange of Zn2+ and Cu2+ over Co2+ and Ni2+ ions in the crystalline solid state when the crystals of 1 are immersed in the aqueous solutions of the perchlorate salts of Cu2+, Zn2+, Co2+, and Ni2+ ions, respectively, which indicates that central CdII ion exchange might be considered as being dominated by the coordination ability of metal ions to free functional groups, ionic radii of exchanged metal ions, and the solution concentration of adsorbed metal salts. The parent material‐ and ion‐exchange‐induced products are identified by FT‐IR spectroscopy, PXRD patterns as well as SEM and EDS measurements. In addition, the thermal stability of 1 was also investigated.

Synthesis, characterization and luminescence properties of polymeric cadmium(II) complexes with imidazole and its derivatives mediated by thiocyanate and dicyanamide anions

Three new polymeric complexes of cadmium(II) with imidazole and its derivatives [imidazole (Im), benzimidazole (Bim) and 1-methylimidazole (Mim)] mediated by thiocyanate and dicyanamide (dca) anions have been synthesized and characterized by X-ray single crystal structure analysis. The structure analyses reveal that complexes [Cd(SCN) 2(Bim) 2] n ( 1) and [Cd(dca) 2(Im) 2] n ( 2) are 1D coordination polymers, whereas complex [Cd(dca) 2(Mim) 2] n ( 3) adopts a 2D network of (4, 4) topology and thereby suggests that the dimensionality of the coordination polymers are affected by the choice of the counter anions and by the organic ligands. All the species exhibit interesting luminescence property in methanol and in solid state originated from ligands-centered π–π* transitions. The π–π interactions occurring between organic rings (Im, Mim, and Bim) are observed to be important in controlling the fluorescence property of the species.

Synthesis, Electronic and IR Spectral Studies of Some Polymeric Cobalt(II), Nickel(II), Zinc(II) and Cadmium(II) Azido Complexes with Hydrazine

A series of polymeric cobalt(II), nickel(II), zinc(II) and cadmium(II) azido complexes with hydrazine of the type [M(N2H4)(H2O)(N3)Cl]n, [M(N2H4)(N3)2]n and [M(N2H4)2(N3)2]n have been prepared. These were characterized by elemental analyses, magnetic susceptibility measurements, electronic and IR spectra. The complexes are highly insoluble in polar and non polar solvents. All the complexes decompose with explosion at different temperatures between 100°C to 200°C. The magnetic moment and electronic spectral data for Co(II) and Ni(II) complexes suggest that the complexes have octahedral structure. The ligand-field parameters (10 Dq, B, β, β° and LFSE) have also been calculated for all Co(II) and Ni(II) complexes which indicate a significant covalent character of M-L bonds. The IR spectra of the complexes show that the azide group and hydrazine molecule both act as bidentate bridging ligands in [M(N2H4)(H2O)(N3)Cl]n and [M(N2H4)(N3)2]n type complexes but the azide group is terminally bonded to metal in all [M(N2H4)2(N3)2]n type complexes.

Synthesis, structures, and luminescent properties of two cadmium polymers of 4-carboxyl phenoxyacetate and 2-(2-pyridyl)benzimidazole

Two-dimensional complexes of [Cd(cpoa)(o-pbim)] n (1) and {[Cd3(cpoa)3(o-pbim)2] · 2H2O} n (2) (cpoa2− = 4-carboxyphenoxy acetate, o-pbim = 2-(2-pyridyl)benzimidazole) are synthesized under hydrothermal condition. Single crystal X-ray diffraction analysis shows that complex 1 contains a mono-nuclear unit, whereas complex 2 contains a trinuclear unit. The structural difference of 1 and 2 can be attributed to the various coordination modes of asymmetrically semi-flexible cpoa2− ligand. The luminescent properties of these two compounds are also investigated.

Synthesis and structure study of a novel 2D network polymeric cadmium(II) complex bridged by thiocyanate

A distorted honeycomb-like cadmium–thiocyanate framework with the formular [BMIM] 2[Cd 2(SCN) 6] has been synthesized by self-assembling through electrostatic interaction between cadmium–thiocyanate network and N,N′-dialkylimidazolium ions. The [BMIM] + cations acting as the spacers and controllers dominate the dimension of the complex.

A Novel Two‐Dimensional Cadmium Polymeric Aminonaphthalene Sulfonate and its Application in the Synthesis of CdS Materials

AbstractA new mixed‐ligand complex, [CdL(bipy)(CH3OH)(NO3)]n (1), (HL = 4‐amino‐1‐naphthalene sulfonic acid and bipy = 4,4′‐bipyridine) could be achieved by combining d10 Cd2+ to HL and bridging ligand 4,4′‐bipy. The structure is characterized by X‐ray single‐crystal diffraction. 4‐amino‐1‐naphthalene sulfonate and 4,4′‐bipyridine act as bridging ligands, linking two adjacent CdII atom to form a two‐dimensional coordination polymer, respectively. N‐H···O hydrogen‐bonding interaction between these networks to form the face‐to‐face three‐dimensional architecture. By carrying out the reaction of polymeric cadmium naphthalene sulfonate with Na2S in the presence of sodium hydroxide, scalelike CdS materials have been obtained. The structure has been characterized by scanning electron microscopy and powder X‐ray diffraction.

Rational Construction of Porous Polymeric Cadmium Ferrocene-1,1′-disulfonates for Transition Metal Ion Exchange and Sorption

Porous pillared bilayer open coordination polymer {[Cd(bpp)2(O3SFcSO3)]·(CH3OH)2 ·(H2O)6}n 1 (Fc = ferrocene) and 3D porous coordination polymer {[Cd(bpy)2(O3SFcSO3)]·(CH3OH)4}n 2 have been assembled from Cd(NO3)2, ferrocene-1,1′-disulfonate, and bridging ligands 1,3-bis(4-pyridyl)propane (bpp) or 4,4′-bipyridine (bpy). Both of them show very special adsorption properties to copper salts. Along with the increase in the solution concentration of Cu(NO3)2, the percentage of adsorbed copper ions falls, but the percentage of exchanged central cadmium ions and the amount of adsorbed copper ions rises. In dilute solution, there mainly exists metal ion sorption, whereas both ion sorption and exchange are in charge of the whole progress in strong solution. Meanwhile, such materials could be used as ideal metal ion adsorbent toward some other metal cations, including of Pb2+, Zn2+, Mn2+, Co2+, Ni2+. However, when all these metal ions coexist in a mixture solution, the two ferrocenyl complexes selectively adsorb la...

Syntheses and Structural Characterization of a One-Dimensional Chain, Two-Dimensional Noninterpenetrated Grid, and Three-Dimensional Polycatenane Coordination Polymers Assembled from Flexible Bidentate Imidazolyl Ligands

Eight novel coordination polymers, [Mn(L 1 ) 2 (H 2 O) 2 ]Cl 2 ·2H 2 O (1, L 1 = bis(N-imidazolyl)methane), [Fe(L 1 ) 2 (NCS) 2 ] (2), [Zn(nba) 2 L 2 ] (3, nba = p-nitrobenzoate, L 2 = 1,4-bis(N-imidazolyl)butane), [Ni(L2)(hba)2(MeOH) 2 ]·2MeOH (4, hba = p-hydroxybenzoate), [Cd(L 2 ) 1.5 (NCS) 2 ] (5), [Cd(L 2 ) 2 (NO 3 ) 2 ] (6), [Cd(L 2 ) 2 (tos) 2 ] (tos = p-tolylsulfonate, 7), and [Ni(L 2 ) 3 ](NO 3 ) 2 (8), were obtained from self-assembly of the corresponding metal salts with the flexible ligands, and their structures were fully characterized. X-ray diffraction analyses revealed that complexes 1 and 2 exhibit one-dimensional (1D) double-stranded chain structures resulting from doubly bridged [Mn(L 1 ) 2 (H 2 O) 2 ] and [Fe(NCS) 2 ], respectively. Complexes 3 and 4 have ID zigzag chain structures in which [Zn(nba) 2 ] and [Ni(hba) 2 (MeOH) 2 ] units are held together by L 2 bridges, respectively. The polymeric cadmium complexes 5-7 have two-dimensional (2D) grid network structures with (4,4) topology. Complex 8 is a cationic polycatenane, and the nitrate anions occupy the triangular channels formed by the interpenetrating networks. Complexes 2, 3, 5, and 6 are stable up to 300 °C. Photoluminescent studies show that complexes 3 and 5-7 display intense blue emissions.

Syntheses, X-ray structures and properties of a dinuclear cadmium(II)azido and a polymeric cadmium(II)thiocyanato compounds containing bis(tridentate) congregators

One-pot reactions of cadmium(II) perchlorate/nitrate, Schiff bases (pbap/pfap) and pseudohalides (sodium azide/ammonium thiocyanate) in a 2:1:4 molar ratio in MeOH–MeCN solvent mixtures at room temperature result in a dinuclear compound [Cd 2(pbap)(OH 2) 2(N 3) 4] ( 1) [pbap = N-(1-pyridin-2-ylbenzylidene)- N-[2-(4-{2-[(1-pyridin-2-ylbenzylidene)amino]ethyl}piperazin-1-yl)ethyl]amine] and a polymeric compound [Cd 2(pfap)(μ 1,3-NCS)(μ 1,3-SCN)(NCS) 2] n ( 2) [pfap = N-(1-pyridin-2-ylformylidene)- N-[2-(4-{2-[(1-pyridin-2ylformylidene)amino]ethyl}piperazin-1-yl)ethyl]-amine]. X-ray crystal structural analyses reveal a bis(tridentate) congregation behaviour of the hexadentate blocker (pbap/pfap) encapsulating two metal centers. Each cadmium(II) center in 1 and 2 is in a distorted octahedral geometry with CdN 5O and CdN 5S chromophores, respectively. In 1, the dinuclear units participate in intermolecular O–H⋯N hydrogen bonding between bound water O atoms and terminal azide N atoms, in combination with C–H⋯π interactions, resulting in a 3D supramolecular network with an intramolecular Cd⋯Cd distance of 6.473(2) Å. In the crystal lattice, the covalent 1D chain of 2 is further engaged in face-to-face π⋯π interactions from two terminal pyridine rings, which stabilizes the chain with an intradimer Cd⋯Cd separation of 6.640(5) Å. Both the complexes display intraligand 1(π–π ∗) fluorescence and intraligand 3(π–π ∗) phosphorescence in glassy solutions.

Syntheses, characterization and antimicrobial activity of the first complexes of Zn(II), Cd(II) and Co(II) with N-benzyloxycarbonylglycine : X-ray crystal structure of the polymeric Cd(II) complex

For the first time, complexes of Zn(II), Cd(II) and Co(II) ( 1– 3) with N-benzyloxycarbonylglycine have been synthesized and characterized. The complexes adopt tetrahedral, pentagonal-bipyramidal and octahedral geometry, respectively. The structure of the polymeric cadmium complex was resolved by single crystal X-ray analysis. The cadmium ion has a distorted pentagonal-bipyramidal coordination formed by two water molecules and two N-benzyloxycarbonylglycinato ligands ( N-Boc) coordinated in different fashions, one as bidentate and the second connecting three cadmium atoms. In a rather complicated 2D supramolecular structure, the phenyl rings interact mutually exclusively by the CH⋯π interactions. Investigation of the antimicrobial activity of the obtained complexes and N-benzyloxycarbonylglycine revealed that the ligand does not inhibit the growth of Candida albicans, whereas the newly synthesized complexes suppress the growth of this human fungal pathogen.

Interactions of thiamine with polymeric halogenocadmate anions in the organic–inorganic hybrid compound (thiaminium)[Cd3Br4.4Cl3.6

The structure of poly[3-[(4-amino-2-methylpyrimidin-1-ium-5-yl)methyl]-5-(2-hydroxyethyl)-4-methylthiazolium octa-mu-bromo/chloro(4.4/3.6)-tricadmate(II)], [(C12H18N4OS)[Cd3 Br4.41Cl3.59]]n consists of hydrogen-bonded thiamine molecules and polymeric cadmium bromide/chloride anions in an organic-inorganic hybrid fashion. The one-dimensional anion ribbons are formed by edge-sharing octahedra and vertex-sharing tetrahedra. Thiamine molecules adopting the S conformation are linked to anions via three types of interactions, namely an N(amino)-H...anion...thiazolium bridging interaction, an N(pyrimidine)-H...anion hydrogen bond and an O(hydroxy)-H...anion hydrogen bond.

Formation and Nonlinear Optical Properties of a Novel Polymeric Cadmium(II) Complex Bridged by Sulfur Ions

Abstract The title coordination polymer, [Cd(NH2NHCSNH2)(HS)2]n·nH2O, has been obtained by self-assembling from the reaction of a methanol/water (volume ratio, 1/1) solution containing cadmium chloride with equivalent amount of succinic acid and thiosemicarbazide. The X-ray crystal analysis reveals that the cadmium atoms are bridged by HS− ligands and mutual sulfur atoms which contribute to formation of the infinite one-dimensional (1D) inorganic–organic chain in a zig-zag way. The second harmonic generation (SHG) response of the complex is much stronger than that of urea.

One‐Dimensional CdII Coordination Polymers: Solid Solutions with NiII, Thermal Stabilities and Structures

AbstractReactions of Cd(NCS)2 with 2‐, 3‐ and 4‐aminobenzonitrile ligands (2ABN, 3ABN and 4ABN respectively) have produced one‐dimensional chain polymers of the general formula [M(NCS)2(ABN)2]n with the metal centres linked by double NCS− bridges. The three cadmium polymers [Cd(NCS)2(3ABN)2]n (1), [Cd(NCS)2(2ABN)2]n (2) and [Cd(NCS)2(4ABN)2]n (3) all differ in their hydrogen‐bonding patterns. In terms of ABN coordination, both 1 and 2 exhibit terminal amine coordination while in 3 the ABNs are coordinated through the cyano groups. Crystalline solid solutions of 1 of general formula [Cd1−xNix(NCS)2(3ABN)2]n, containing nickel and cadmium in varying proportions, have also been prepared in order to establish the influence of the metal ratio on the thermal stability and bonding parameters of the polymers. The coordination polymers are not good candidates for forming clathrates while their thermal stability (ranging between 147 and 244 °C) depends on the position of functional groups on the ABN ligands and on the Cd:Ni ratio in the solid solutions. The new polymers have been characterised by single crystal X‐ray diffraction, X‐ray powder diffraction, electron microscopy, infrared spectroscopy, thermogravimetry and differential scanning calorimetry. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

The Effect of Water–Ethanol Solvent on the Deposition Kinetics and Tribological Characteristics of Cadmium–Polymer Coatings

It is shown how the liquid phase composition, the nature of particles adsorbed and reduced at the electrode, and e-caprolactam (CPL) additive affect the electroreduction of cadmium ions and resistance of cadmium–polymer coatings to wear. The acceleration of the electrode process in the presence of CPL in aqueous electrolyte and in a range of microheterogeneous water–ethanol solvent is attributed to the electroreduction of adsorbed cadmium (II) complexes in which CPL molecules act as bridge ligands. In a range of water-structure stability, the main reason for promoted discharge of complex cations preceded by their dissociation in the bulk solution is the Ψ′ effect associated with an increase in perchlorate ion adsorption on Cd. The “forced” mechanism of the complex species dissociation at the cathode in a bath with high concentration of nonaqueous solvent makes the CPL-induced acceleration give way to inhibition. Cadmium–polymeric coatings formed as a result of the co-adsorption of CPL and nonaqueous component molecules (i.e., in the range of water stabilization and maximum microheterogeneity of the mixed solvent) exhibit the maximum wear resistance.

Complexes of heterocyclic thiones and group 12 metals: Part VI. Preparation and characterisation of complexes of cadmium(II) halides with 1-methylimidazoline-2(3H)-thione, 1,3-thiazolidine-2-thione and 1,3-benzothiazoline-2-thione. Crystal structures of polymeric (1,3-thiazolidine-2-thione)cadmium(II) chloride, bis(1,3-thiazolidine-2-thione)cadmium(II) iodide and monomeric bis(1-methylimidazoline-2(3H)-thione)cadmium(II) bromide

Reactions of 1-methylimidazoline-2(3H)-thione (meimz2SH), 1,3-thiazolidine-2-thione (tzdSH) and 1,3-benzothiazoline-2-thione (bztzSH) with cadmium(II) halides in ethanol solutions result in the formation of 1:1 complexes for the chloride, both 1:1 and 2:1 complexes for the bromide, and only 2:1 complexes for the iodide. Spectroscopic evidence confirms the exocyclic sulfur atom to be the donor in all cases. Cadmium(II) acetate and the heterocyclic ligands in the presence of triethylamine form the insoluble deprotonated complexes. The structure of (tzdSH)CdCl 2 consists of double halogen-bridged chains, linked into sheets via NH⋯Cl interactions and with the heterocycle coordinated to the metal via the exocyclic sulfur atom. Thus each cadmium is approximately octahedrally surrounded by one sulfur, 2 two-coordinate and 3 three-coordinate chlorine atoms. In contrast (tzdSH) 2CdI 2 forms chains via I⋯S interactions; the metal is tetrahedrally coordinated by two sulfur and two iodine atoms. The structure of (meimz2SH) 2CdBr 2 consists of discrete complex molecules with essentially tetrahedrally coordinated Cd and no significant intermolecular interactions; the six molecules in the asymmetric unit are related by pseudo-symmetry and are very similar except for variation in the orientation of the heterocyclic substituents.

Formation of a Novel Polymeric Cadmium(II) Complex Bridged by Sulfur and Thiocyanato Ions.

AbstractFor Abstract see ChemInform Abstract in Full Text.