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SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni)

Year 2016, Volume: 17 Issue: 1, 37 - 49, 05.01.2016
https://doi.org/10.18038/btda.57780

Abstract

In this study, cyanide complexes with chemical formula [M(hepH)2Ni(μ-CN)2(CN)2] (hepH = 2-pyridineethanol; M = Fe(II), Co(II) and Ni(II); abbreviated to hereafter M-hepH-Ni) were obtained for the first time. The structures of these complexes were determined by using FT-IR and Raman spectroscopies, thermal and elemental analyses. The electrical and magnetic properties of the complexes were investigated by four-probe and Evans methods, respectively. Vibration assignments have been obtained for all the observed bands and the spectral features were observed supported to the structures of complexes. Thermal behaviors of the complexes were examined using TG, DTG and DTA curves in the temperature range 30 - 700 °C in the static air atmosphere. According to thermal analysis curves, it has seen that neutral ligands (hepH) are released and cyanide ligands are decomposed in the complexes, followed usual decomposition mechanism. The final decomposition products have been found to be the metal oxides. The magnetic measurements of the complexes were compared with experimental and theoretical values of the magnetic moment. Furthermore, Fe-hepH-Ni, Co-hepH-Ni and Ni-hepH-Ni complexes were determined to be paramagnetic. 

References

  • Batten SR, Neville SM, Turner DR. Coordination polymers: design, analysis and application. Royal Society of Chemistry:Cambridge, UK, 2009.
  • Janiak C. Engineering coordination polymers towards applications. Dalton Trans 2003; 14: 2781
  • Korkmaz ŞA, Karadağ A, Yerli Y, Soylu MS. Synthesis and characterization of new heterometallic cyanido complexes based on [Co(CN)6]3− bishydeten)2Co(CN)6]·3H2O having a strong antiferromagnetic exchange. New J Chem. 2014: 38; 5402- building blocks: crystal structure of [Cu2(N
  • Černák J, Orendáč M, Potočňák I, Chomič J, Orendáčová A, Skoršepa J, Feher A. Cyanocomplexes with one-dimensional structures: preparations, crystal structures and magnetic properties. Coord Chem Rev 2002; 224: 51-66.
  • Kajňaková M, Černák J, Kavečanský V, Gérard F, Papageorgiou T, Orendáč M, Orendáčová A, Feher A. Magneto-structural correlations. Rietveld refinement of the three-dimensional crystal structure of Mn(en)Ni(CN)(en= ethylenediamine) and magnetic interactions through the [Ni(CN)4] anion. Solid State Sci 2006: 8: 203-207.
  • Ouahab L, Setifi F, Golhen S, Imakubo T, Lescouëzec R, Lloret F, Julve M, Świetlik R. Charge transfer salts containing a paramagnetic cyano-complex and iodine substituted organic donor involving -I(donor)··· N(anion)- interactions. C R Chim 2005: 8; 1286-1297.
  • González M, Lemus-Santana A, Rodríguez-Hernández J, Knobel M, Reguera E. π···π interactions and magnetic properties in a series of hybrid inorganic–organic crystals. J Solid State Chem 2013; 197: 317
  • Hoskins B, Robson R. Design and construction of a new class of scaffolding-like materials comprising infinite polymeric frameworks of 3D-linked molecular rods. A reappraisal of the zinc cyanide and cadmium cyanide structures and the synthesis and structure of the diamond-related frameworks N(CH3)4][CuIZnII(CN)4] and CuI[4, 4', 4'', 4'''-tetracyanotetraphenylmethane]BF4·xC6H5NO2. J Am Chem Soc 1990; 112: 1546-1554.
  • Herebian D, Wieghardt KE, Neese F. Analysis and Interpretation of Metal-Radical Coupling in a Series of Square Planar Nickel Complexes: Correlated Ab Initio and Density Functional Investigation of Ni(LISQ)2](LISQ= 3, 5-di-tert-butyl-o-diiminobenzosemiquinonate (1-)). J Am Chem Soc 2003; 125: 10997
  • Lescouëzec R, Lloret F, Julve M, Vaissermann J, Verdaguer M. [Fe(bipy)(CN)4]- as a versatile building block for the design of heterometallic systems: synthesis, crystal structure, and magnetic properties {FeIII(bipy)(CN)4}2ZnII]·2H2O [bipy = 2, 2'-Bipyridine; M= Mn and Zn]. Inorg Chem 2002; 41: 818-826.
  • PPh[FeIII(bipy)(CN)4]·H2O, {FeIII(bipy)(CN)4}2MII(H2O)4]·4H2O, and Bullinger JC, Moore CE, Eichhorn DM. Recent advances in cyanoscorpionate chemistry: complexes with Co(II), Mn(II), and Ni(II)(cyclam). Proceedings of the 4th Annual GRASP Symposium; 25 April 2008; Wichita, KS: Wichita State University, p.23-24
  • Sayın E, Kürkçüoğlu GS, Yeşilel OZ, Hökelek T. C-H⋯Pd interactions: One dimensional heteropolynuclear complexes. Spectrochim Acta Part A 2014; 132: 803-814.
  • Sayın E, Kürkçüoğlu GS, Yeşilel OZ, Hökelek T. Syntheses and characterizations of tetracyanoplatinate(II) complexes with 2-pyridineethanol. J Coord Chem 2015; 68: 2271-2285.
  • Kürkçüoğlu GS, Sayın E, Gör K, Arslan T, Büyükgüngör O. C-H⋯Ni Interactions and Cyano- Bridged Heteronuclear Polymeric Complexes Studied by Vibrational Spectroscopy and Quantum Chemistry Calculations. Vib Spectrosc 2014; 71: 105-117.
  • Aggarwal K, Khurana JM. X-ray diffraction, spectroscopic characterization and quantum chemical calculations by DFT and HF of novel 2-hydroxy-12-(4-hydroxyphenyl)-9,9-dimethyl-9,10- dihydro-8H-benzo[a]xanthen-11(1 H)-one. J Mol Struct 2015;1079: 21-34.
  • Michalska D, Bienko D, Abkowicz-Bienko A, Latajka Z. Density functional, Hartree-Fock, and MP2 studies on the vibrational spectrum of phenol. J Phys Chem 1996; 100: 17786-17790.
  • Arjunan V, Balamourougane PS, Govindaraja ST, Mohan S. A comparative study on vibrational, conformational and electronic structure of 2-(hydroxymethyl)pyridine and 3-(hydroxymethyl)pyridine. J. Mol. Struct 2012; 1018: 156-170.
  • Socrates G, Infrared and Raman characteristic group frequencies: tables and charts. 3rd ed. John Wiley & Sons, Chichester, England, 2004.
  • Varsányi G, Assignments for vibrational spectra of seven hundred benzene derivatives. 1. Halsted Press, Wiley-Interscience: New York, 1974.
  • Arjunan V, Mohan S. Fourier transform infrared and FT-Raman spectra, assignment, ab initio, DFT and normal co-ordinate analysis of 2-chloro-4-methylaniline and 2-chloro-6-methylaniline. Spectrochim Acta Part A 2009; 72: 436-444.
  • Arjunan V, Puviarasan N, Mohan S, Fourier transform infrared and Raman spectral investigations of 5-aminoindole. Spectrochim Acta Part A 2006; 64: 233-239.
  • Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds. Part B., Applications in coordination, organometallic, and bioinorganic chemistry. 6th ed. John Wiley&Sons, Hoboken, New Jersey, 2009.
  • McCullough R, Jones L, Crosby G. An analysis of the vibrational spectrum of the tetracyanonickelate(II) ion in a crystal lattice. Spectrochim Acta 1960; 16: 929-944.
  • Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds.3rd ed. Wiley, New York, 1978.
  • Bignozzi CA, Argazzi R, Schoonover JR, Gordon KC, Dyer RB, Scandola F. Electronic coupling in cyano-bridged ruthenium polypyridine complexes and role of electronic effects on cyanide stretching frequencies. Inorg Chem 1992; 31: 5260-5267.
  • Kubas GJ, Jones, LH. Potential constants of the tetracyanide ions of nickel, palladium, and platinum. Inorg Chem 1974; 13: 2816-2819.
  • Vitoria P, Beitia JI, Gutiérrez-Zorrilla JM, Sáiz ER, Luque A, Insausti M, Blanco JJ. Tetracyanometalates of Ni, Pd, and Pt with cyclic diquaternary cations of 2, 2'-bipyridine and 1, 10- phenanthroline. A vibrational, crystallographic, and theoretical study of intermolecular weak interactions. Inorg Chem 2002; 41: 4396-4404.
  • Parlak C. FT-IR and Raman spectroscopic analysis of some Hofmann type complexes. Spectrochim Acta Part A 2012; 99: 12-17.
  • Hanack M, Polley R, Knecht S, Schlick U. Reaction of cyanogen with cobalt phthalocyanines. Inorg Chem 1995; 34: 3621-3624.
  • Hanack M, Hirsch A, Lange A, Rein M, Renz G, Vermehren P. Bridged macrocyclic transition metal complexes, a new type of semiconducting materials. J Mater Res 1991; 6: 385-392.
  • Kürkçüoğlu GS, Kiraz FÇ, Sayın E. Vibrational spectra, powder X-ray diffractions and physical properties of cyanide complexes with 1-ethylimidazole. Spectrochim Acta Part A 2015; 149: 8-16.
  • Karadağ A, Yılmaz VT. Preparation and Infrared Spectroscopic Examination of Hofmann-Type Di-and Triethanolamine Complexes. Synth React Inorg Met -Org Chem 2000; 30: 359-368.

2-PİRİDİNETANOL İLE SİYANÜR-KÖPRÜLÜ M(II)-Ni(II) İKİ METALLİ KOMPLEKSLERİN SENTEZİ, YAPISI VE FİZİKSEL ÖZELLİKLERİ (M(II) = Fe, Co ve Ni)

Year 2016, Volume: 17 Issue: 1, 37 - 49, 05.01.2016
https://doi.org/10.18038/btda.57780

Abstract

Bu çalışmada [ML2Ni(μ-CN)2(CN)2] (L= 2-piridinetanol (hepH); M = Fe(II), Co(II) veya Ni(II); bundan sonra M-hepH-Ni olarak kısaltılmıştır.) formülü ile verilen siyanür kompleksleri ilk kez elde edilmiştir. Bu komplekslerin yapıları kırmızı-altı ve Raman spektroskopisi, termal ve elementel analiz teknikleri kullanılarak belirlenmiştir. Komplekslerin elektriksel özellikleri dört uç metodu, manyetik özellikleri ise Evans metodu kullanılarak araştırılmıştır. Titreşim işaretlemeleri tüm gözlenen bandlar için elde edilmiş ve spektral özelliklerin komplekslerin yapılarını destekledikleri görülmüştür. Komplekslerin termal davranışları kuru havada 30 - 700 ºC sıcaklık aralığında TG, DTG ve DTA eğrileri kullanılarak incelenmiştir. Termal analiz eğrilerine göre, hepH ligandının ve siyanür grubunun yapılardan uzaklaştıkları görülmüştür. Son bozunma ürünlerinin metal oksitler olduğu bulunmuştur. Manyetik ölçümlerde komplekslerin deneysel ve teorik manyetik moment değerleri karşılaştırılmıştır. Ayrıca, Fe-hepH-Ni, Co-hepH-Ni ve Ni-hepH-Ni komplekslerinin paramanyetik oldukları belirlenmiştir.

References

  • Batten SR, Neville SM, Turner DR. Coordination polymers: design, analysis and application. Royal Society of Chemistry:Cambridge, UK, 2009.
  • Janiak C. Engineering coordination polymers towards applications. Dalton Trans 2003; 14: 2781
  • Korkmaz ŞA, Karadağ A, Yerli Y, Soylu MS. Synthesis and characterization of new heterometallic cyanido complexes based on [Co(CN)6]3− bishydeten)2Co(CN)6]·3H2O having a strong antiferromagnetic exchange. New J Chem. 2014: 38; 5402- building blocks: crystal structure of [Cu2(N
  • Černák J, Orendáč M, Potočňák I, Chomič J, Orendáčová A, Skoršepa J, Feher A. Cyanocomplexes with one-dimensional structures: preparations, crystal structures and magnetic properties. Coord Chem Rev 2002; 224: 51-66.
  • Kajňaková M, Černák J, Kavečanský V, Gérard F, Papageorgiou T, Orendáč M, Orendáčová A, Feher A. Magneto-structural correlations. Rietveld refinement of the three-dimensional crystal structure of Mn(en)Ni(CN)(en= ethylenediamine) and magnetic interactions through the [Ni(CN)4] anion. Solid State Sci 2006: 8: 203-207.
  • Ouahab L, Setifi F, Golhen S, Imakubo T, Lescouëzec R, Lloret F, Julve M, Świetlik R. Charge transfer salts containing a paramagnetic cyano-complex and iodine substituted organic donor involving -I(donor)··· N(anion)- interactions. C R Chim 2005: 8; 1286-1297.
  • González M, Lemus-Santana A, Rodríguez-Hernández J, Knobel M, Reguera E. π···π interactions and magnetic properties in a series of hybrid inorganic–organic crystals. J Solid State Chem 2013; 197: 317
  • Hoskins B, Robson R. Design and construction of a new class of scaffolding-like materials comprising infinite polymeric frameworks of 3D-linked molecular rods. A reappraisal of the zinc cyanide and cadmium cyanide structures and the synthesis and structure of the diamond-related frameworks N(CH3)4][CuIZnII(CN)4] and CuI[4, 4', 4'', 4'''-tetracyanotetraphenylmethane]BF4·xC6H5NO2. J Am Chem Soc 1990; 112: 1546-1554.
  • Herebian D, Wieghardt KE, Neese F. Analysis and Interpretation of Metal-Radical Coupling in a Series of Square Planar Nickel Complexes: Correlated Ab Initio and Density Functional Investigation of Ni(LISQ)2](LISQ= 3, 5-di-tert-butyl-o-diiminobenzosemiquinonate (1-)). J Am Chem Soc 2003; 125: 10997
  • Lescouëzec R, Lloret F, Julve M, Vaissermann J, Verdaguer M. [Fe(bipy)(CN)4]- as a versatile building block for the design of heterometallic systems: synthesis, crystal structure, and magnetic properties {FeIII(bipy)(CN)4}2ZnII]·2H2O [bipy = 2, 2'-Bipyridine; M= Mn and Zn]. Inorg Chem 2002; 41: 818-826.
  • PPh[FeIII(bipy)(CN)4]·H2O, {FeIII(bipy)(CN)4}2MII(H2O)4]·4H2O, and Bullinger JC, Moore CE, Eichhorn DM. Recent advances in cyanoscorpionate chemistry: complexes with Co(II), Mn(II), and Ni(II)(cyclam). Proceedings of the 4th Annual GRASP Symposium; 25 April 2008; Wichita, KS: Wichita State University, p.23-24
  • Sayın E, Kürkçüoğlu GS, Yeşilel OZ, Hökelek T. C-H⋯Pd interactions: One dimensional heteropolynuclear complexes. Spectrochim Acta Part A 2014; 132: 803-814.
  • Sayın E, Kürkçüoğlu GS, Yeşilel OZ, Hökelek T. Syntheses and characterizations of tetracyanoplatinate(II) complexes with 2-pyridineethanol. J Coord Chem 2015; 68: 2271-2285.
  • Kürkçüoğlu GS, Sayın E, Gör K, Arslan T, Büyükgüngör O. C-H⋯Ni Interactions and Cyano- Bridged Heteronuclear Polymeric Complexes Studied by Vibrational Spectroscopy and Quantum Chemistry Calculations. Vib Spectrosc 2014; 71: 105-117.
  • Aggarwal K, Khurana JM. X-ray diffraction, spectroscopic characterization and quantum chemical calculations by DFT and HF of novel 2-hydroxy-12-(4-hydroxyphenyl)-9,9-dimethyl-9,10- dihydro-8H-benzo[a]xanthen-11(1 H)-one. J Mol Struct 2015;1079: 21-34.
  • Michalska D, Bienko D, Abkowicz-Bienko A, Latajka Z. Density functional, Hartree-Fock, and MP2 studies on the vibrational spectrum of phenol. J Phys Chem 1996; 100: 17786-17790.
  • Arjunan V, Balamourougane PS, Govindaraja ST, Mohan S. A comparative study on vibrational, conformational and electronic structure of 2-(hydroxymethyl)pyridine and 3-(hydroxymethyl)pyridine. J. Mol. Struct 2012; 1018: 156-170.
  • Socrates G, Infrared and Raman characteristic group frequencies: tables and charts. 3rd ed. John Wiley & Sons, Chichester, England, 2004.
  • Varsányi G, Assignments for vibrational spectra of seven hundred benzene derivatives. 1. Halsted Press, Wiley-Interscience: New York, 1974.
  • Arjunan V, Mohan S. Fourier transform infrared and FT-Raman spectra, assignment, ab initio, DFT and normal co-ordinate analysis of 2-chloro-4-methylaniline and 2-chloro-6-methylaniline. Spectrochim Acta Part A 2009; 72: 436-444.
  • Arjunan V, Puviarasan N, Mohan S, Fourier transform infrared and Raman spectral investigations of 5-aminoindole. Spectrochim Acta Part A 2006; 64: 233-239.
  • Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds. Part B., Applications in coordination, organometallic, and bioinorganic chemistry. 6th ed. John Wiley&Sons, Hoboken, New Jersey, 2009.
  • McCullough R, Jones L, Crosby G. An analysis of the vibrational spectrum of the tetracyanonickelate(II) ion in a crystal lattice. Spectrochim Acta 1960; 16: 929-944.
  • Nakamoto K. Infrared and Raman spectra of inorganic and coordination compounds.3rd ed. Wiley, New York, 1978.
  • Bignozzi CA, Argazzi R, Schoonover JR, Gordon KC, Dyer RB, Scandola F. Electronic coupling in cyano-bridged ruthenium polypyridine complexes and role of electronic effects on cyanide stretching frequencies. Inorg Chem 1992; 31: 5260-5267.
  • Kubas GJ, Jones, LH. Potential constants of the tetracyanide ions of nickel, palladium, and platinum. Inorg Chem 1974; 13: 2816-2819.
  • Vitoria P, Beitia JI, Gutiérrez-Zorrilla JM, Sáiz ER, Luque A, Insausti M, Blanco JJ. Tetracyanometalates of Ni, Pd, and Pt with cyclic diquaternary cations of 2, 2'-bipyridine and 1, 10- phenanthroline. A vibrational, crystallographic, and theoretical study of intermolecular weak interactions. Inorg Chem 2002; 41: 4396-4404.
  • Parlak C. FT-IR and Raman spectroscopic analysis of some Hofmann type complexes. Spectrochim Acta Part A 2012; 99: 12-17.
  • Hanack M, Polley R, Knecht S, Schlick U. Reaction of cyanogen with cobalt phthalocyanines. Inorg Chem 1995; 34: 3621-3624.
  • Hanack M, Hirsch A, Lange A, Rein M, Renz G, Vermehren P. Bridged macrocyclic transition metal complexes, a new type of semiconducting materials. J Mater Res 1991; 6: 385-392.
  • Kürkçüoğlu GS, Kiraz FÇ, Sayın E. Vibrational spectra, powder X-ray diffractions and physical properties of cyanide complexes with 1-ethylimidazole. Spectrochim Acta Part A 2015; 149: 8-16.
  • Karadağ A, Yılmaz VT. Preparation and Infrared Spectroscopic Examination of Hofmann-Type Di-and Triethanolamine Complexes. Synth React Inorg Met -Org Chem 2000; 30: 359-368.
There are 32 citations in total.

Details

Primary Language English
Subjects Engineering
Journal Section Articles
Authors

Elvan Sayın

Güneş Süheyla Kürkçüoğlu

Publication Date January 5, 2016
Published in Issue Year 2016 Volume: 17 Issue: 1

Cite

APA Sayın, E., & Kürkçüoğlu, G. S. (2016). SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni). Anadolu University Journal of Science and Technology A - Applied Sciences and Engineering, 17(1), 37-49. https://doi.org/10.18038/btda.57780
AMA Sayın E, Kürkçüoğlu GS. SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni). AUJST-A. June 2016;17(1):37-49. doi:10.18038/btda.57780
Chicago Sayın, Elvan, and Güneş Süheyla Kürkçüoğlu. “SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni)”. Anadolu University Journal of Science and Technology A - Applied Sciences and Engineering 17, no. 1 (June 2016): 37-49. https://doi.org/10.18038/btda.57780.
EndNote Sayın E, Kürkçüoğlu GS (June 1, 2016) SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni). Anadolu University Journal of Science and Technology A - Applied Sciences and Engineering 17 1 37–49.
IEEE E. Sayın and G. S. Kürkçüoğlu, “SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni)”, AUJST-A, vol. 17, no. 1, pp. 37–49, 2016, doi: 10.18038/btda.57780.
ISNAD Sayın, Elvan - Kürkçüoğlu, Güneş Süheyla. “SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni)”. Anadolu University Journal of Science and Technology A - Applied Sciences and Engineering 17/1 (June 2016), 37-49. https://doi.org/10.18038/btda.57780.
JAMA Sayın E, Kürkçüoğlu GS. SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni). AUJST-A. 2016;17:37–49.
MLA Sayın, Elvan and Güneş Süheyla Kürkçüoğlu. “SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni)”. Anadolu University Journal of Science and Technology A - Applied Sciences and Engineering, vol. 17, no. 1, 2016, pp. 37-49, doi:10.18038/btda.57780.
Vancouver Sayın E, Kürkçüoğlu GS. SYNTHESES, STRUCTURES AND PHYSICAL PROPERTIES OF CYANIDE-BRIDGED M(II)−Ni(II) BIMETALLIC COMPLEXES WITH 2-PYRIDINEETHANOL (M(II) = Fe, Co and Ni). AUJST-A. 2016;17(1):37-49.