Syntheses, IR spectra, thermal properties and crystal structures of novel cyano-bridged polymeric complexes of zincII and cadmiumII with tetracyanoplatinateII (original) (raw)
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Journal of Inorganic and Organometallic Polymers and Materials, 2011
Characterization and synthesis of novel cyano bridged coordination compounds [Ni(bishydeten)Pt(CN) 4 ] (1), [Cu(bishydeten)Pt(CN) 4 ] (2), [Zn(bishydeten)Pt(CN) 4 ] (3), [Cd(bishydeten)Pt(CN) 4 ] (4) [bishydeten = N,N 0-bis(2hydroxyethyl)ethylenediamine (C 6 H 16 N 2 O 2)] were reported herein. The IR spectra of these coordination compounds verified the formation of aforementioned complexes. The ground state of the paramagnetic electron in the Cu II located in tetragonal distorted octahedral sites (D 4h) was found to be d x2-y2 for complex 2. As for complex 1, an EPR signal was not observed because of diamagnetic property of the Pt II and momentary relaxation times of the Ni II. All complexes followed identical decomposition mechanism in thermal analysis and thermal stabilities of complexes changed in the order of 1 [ 4 [ 3 [ 2. Both 3 and 4 exhibit polymeric structure according to X-ray single structure analysis. While bishydeten coordinated with three donor atoms (N,N 0 , and O) in complex 3, it acts as a bidentate ligand (N, and N 0) in complex 4. Magnetic properties of complexes 1-2 at 15-300 K temperature range were determined as antiferromagnetic with Weiss constants =-2.619 and-0.847 K respectively. Keywords Cyano bridged polymers Á EPR Á Magnetic susceptibility Á Thermal analysis Á N,N 0-bis(2-hydroxyethyl)ethylenediamine Á Tetracyanoplatinate II
Network topologies and properties of cyanoplatinate coordination polymers
2019
This work is a contribution to the rich literature on cyanoplatinate chemistry, with a focus on the synthesis and materials properties of coordination polymers that incorporate [Pt(CN) 4 ] 2and [PtX 2 (CN) 4 ] 2-(X = Cl, Br) as linkers. Furthermore, fundamental Pt 2+ chemistry is explored in the synthesis of new linkers incorporating the ligand isomaleonitriledithiolate (i-mnt) for use in chemical sensors and negative thermal expansion materials. Combination of M 2+ with [PtX 2 (CN) 4 ] 2-(X = Cl, Br) results in the formation of solventtemplated coordination polymers with networks of varying hydration, M(H 2 O) n [PtX 2 (CN) 4 ]•mH 2 O (n = 0 to 2; m = 0 to 8). The structures of the coordination polymers are described; characterization methods include IR, Raman, TGA, EA, and variable temperature XRD. A comparative study between the thermal expansion properties of Cu(H 2 O) 2 [PtX 2 (CN) 4 ] and Cu[PtX 2 (CN) 4 ] highlights the impact of solvent on the thermal expansion of these materials. The ability of Cu(H 2 O) 2 [PtX 2 (CN) 4 ] (X = Cl, Br) to act as vapochromic sensors and their vapour adducts Cu(L) 2 [PtX 2 (CN) 4 ] (L = DMSO, DMF, Pyridine; X = Cl, Br) are reported. Some simple amine-containing compounds were also prepared, and a detailed analysis carried out on the solid state NMR of pyrazinecontaining M(H 2 O) 2 [PtBr 2 (CN) 4 ]•2pyz (M = Co 2+ , Zn 2+ , and Cd 2+) and Cu(pyz)[PtBr 2 (CN) 4 ] compounds. The structures, optical, and thermal properties of new [Pt(CN) 4 ] 2coordination polymers prepared by combination with Pb 2+ , Cd 2+ , and Mn 2+ are reported. The interplay between the Pt 4+ halogenated and Pt 2+ non-halogenated materials for X 2 (X = Cl, Br) sensing is also studied. Attempts to isolate [Pt(i-mnt) 2 ] 2and combination with d 10 M 2+ for chemical sensors, and conditions for oxidation to [Pt(i-mnt) 3 ] 2are discussed. A series of new asymmetric i-mntcontaining Pt complexes have also been prepared. Metal organic frameworks formed from the combination of the Pd 2+ analogues and M 2+ , M(H 2 O) 4 [Pd(i-mnt) 2 ] (M = Mn 2+ , Co 2+ , Zn 2+), have also been prepared and fully characterized.
Structural Chemistry, 2008
The cyano-bridged heteronuclear polymeric complex, [Cd(teta)Ni(l-CN) 2 (CN) 2 ] Á 2H 2 O (1), (teta = triethylenetetraamine) was synthesized and characterized by FT-IR spectroscopy, thermal analysis and single crystal X-ray diffraction techniques. It crystallizes in the orthorhombic system, space group Pccn. The asymmetric unit also contains two uncoordinated water molecules. The coordination geometry around the Cd(II) centre is a highly distorted octahedral. In the crystal structure, intramolecular N-HÁÁÁO and intermolecular N-HÁÁÁO, O-HÁÁÁO and O-HÁÁÁN hydrogen bonds, beside the cyano-bridged chains made up of tetracyanonickelate ions coordinated to Cd(II) ions, where the Ni(II) ion is coordinated by four cyanoligands in a square-planar arrangement, link the molecules into polymeric networks parallel to (001) plane, where the hydrogen bonded water molecules occupy the cavities between the layers. The FT-IR spectrum was reported in the 4,000-400 cm-1 region. Vibration assignments were given for all the observed bands and the spectral feature also supported the structure of the polymeric complex. The decomposition reaction takes place in the temperature range 20-1,000°C in the static air atmosphere.
C−H⋯Pd interactions and cyano-bridged heteronuclear polymeric complexes
Polyhedron
Three new heterometallic complexes, [Cu(N-Meim)4Pd(μ-CN)2(CN)2]n (1), [Zn(N-Meim)3Pd(μ-CN)2(CN)2]n (2) and [Cd(N-Meim)2Pd(μ-CN)4]n (3), have been isolated from the reactions of M[Pd(CN)4] (M = Cu(II), Zn(II) or Cd(II)) and N-Meim (N-methylimidazole) with in different molar ratios. All complexes have been characterized by X-ray analyses, vibrational (FT-IR and Raman) spectra, thermal and elemental analyses. The crystallographic analysis reveals that the crystal structures of 1 and 2 are 1D coordination polymer, while 3 presents a 2D network. In the Cu(II) and Zn(II) complexes, two cyanide groups of [Pd(CN)4]2− coordinated to the adjacent M(II) ions and distorted octahedral and square pyramidal geometries of complexes are completed by four and three nitrogen atoms of N-Meim ligands, respectively. The Cd(II) ion is six-coordinate, completed with the two nitrogen atoms of N-Meim ligands in the axial positions and the four nitrogen atoms from bridging cyano groups in the equatorial plane. The most striking features of complexes 1–3 are the presence of obvious C–H⋯Pd hydrogen-bonding interactions between the Pd(II) and hydrogen atoms of N-Meim ligand. This weak hydrogen bonding plays a crucial role in the architecture of the network polymers. The adjacent chains are held together by C–H⋯Pd, C–H⋯π or π⋯π interactions, forming three-dimensional network.Three new heterometallic complexes, [Cu(N-Meim)4Pd(μ-CN)2(CN)2]n (1), [Zn(N-Meim)3Pd(μ-CN)2(CN)2]n (2) and [Cd(N-Meim)2Pd(μ-CN)4]n (3), have been isolated from the reactions of M[Pd(CN)4] (M = Cu(II), Zn(II) or Cd(II)) and N-Meim (N-methylimidazole) with in different molar ratios. The most striking features of complexes are the presence of obvious C−H···Pd hydrogen-bonding interactions between the Pd(II) and hydrogen atoms of N-Meim ligand. This weak hydrogen bonding plays a crucial role in the architecture of the network polymers. The adjacent chains are held together by C–H⋯Pd, C–H⋯π or π⋯π interactions, forming three-dimensional network.
Inorganica Chimica Acta, 2014
Violet crystals of [Cu 2 (teta) 2 Pt(CN) 4 ] 2 [Pt(CN) 4 ] 2 (1, teta = N,N'-bis(2-aminoethyl)-1,2-diaminoethane; triethylenetetramine) and {[Cu 3 (bapen) 3 Pt(CN) 4 ][Pt(CN) 4 ] 2 Á13H 2 O} n (2, bapen = N,N 0-bis(3-aminopropyl)-1,2-diaminoethane) were crystallized from the water-methanol or aqueous solutions containing Cu(II) salt, teta or bapen ligand and K 2 [Pt(CN) 4 ]. Both compounds were characterized using elemental analysis, IR and UV-Vis spectroscopy, thermal and X-ray crystal structure analysis. Two m(C"N) absorption bands in the IR spectra of the complexes imply non-equivalency of cyanido groups meaning the presence of both, terminal and bridging ones and together with the results of elemental analysis indicate simple chain-like structure. Thermal decompositions of the prepared complexes are few-step processes which comprise liberation of crystal water (only for 2), decay of N-donor ligands L and release of cyanido groups. Finally, an X-ray crystal structure analysis has shown their complicated crystal structures. On one hand, complex 1 is of ionic character and is formed from a couple of trinuclear [Cu(teta)-Pt(CN) 4-Cu(teta)] 2+ complex cations and a couple of discrete [Pt(CN) 4 ] 2À anions. On the other hand, complex 2 is of polymeric character and is formed by 1D chains of {[Cu 3 (bapen) 3 Pt(CN) 4 ] 4+ } n composition, 2n single [Pt(CN) 4 ] 2À anions and 13n molecules of crystal water.
2014
Polymeric copper(II), zinc(II) and cadmium(II) complexes of polydentate ligand 1,5-bis(2- pyrimidineaminoethylidene)-2,4-dihydroxy benzene (H2bispdb) and 1,5-bis(p-tolylaminoethylidene)-2,4- dihydroxy benzene (H2bistdb) of compositions (CuL(H2O)2)n and (ML)n, (M= Zn II or Cd II and H2L= H2bispdb or H2bistdb) were synthesised and characterised by analytical results, magnetic susceptibility, 1 HNMR, IR and electronic absorption studies. The thermal stability of zinc(II) and copper(II) complexes were studied and discussed.
Journal of Molecular Structure, 2009
Nickel(II)Á Á Áp interaction in [M(ampy) 2 Ni(l-CN) 2 (CN) 2 ] n (M = Zn(II) and Cd(II), ampy = 2-aminomethylpyridine): Syntheses, vibrational spectroscopy, thermal analyses and crystal structures of cyano-bridged heteronuclear polymeric complexes Günes ß Süheyla Kürkçüoglu a, * , Okan Zafer Yes ßilel b , _