M(4-Pridinkarboksialdehid)Ni(CN)4.nG Hofmann Tipi Konak-Konuk Bileşiklerinin Kırmızıaltı Spektroskopik Özelliklerinin İncelenmesi (M = Ni, Cd ve G = 1,4-Dioksan)

Bu çalışmada ilk kez toz şeklinde elde edilen M(4-Pridinkarboksialdehid)Ni(CN)4.nG (M = Ni, Cd ve G = 1,4-dioksan) klatratlarının kırmızıaltı spektrumları (3000–400) cm-1 spektroskopik bölgesinde alınarak soğurma titreşim modları ve onların tanımlamaları yapıldı. Bu tanımlamalar literatürde yer alan diğer Hofmann-tipi klatratlar ile karşılaştırıldı ve benzer sonuçlar gözlendi. Bu çalışmamızdaki Hofmann tipi dioksan klatratları 4- pridinkarboksialdehid ligand molekülünün piridin halkası üzerindeki azot atomu ve aldehit (-CH=O) grubunun oksijen atomunun geçiş metali atomlarına bağlanmasıyla oluştuğu ve |M–Ni(CN)4| polimerik tabakalarının ise (–M–4PCA–M–) zincirleri tarafından paralel halde tutulduğu anlaşılmıştır. Bu çalışma sonucunda Hofmann-tipi klatratlara iki yeni örnek kazandırılmıştır.

Anahtar Kelimeler:

Kırmızıaltı Spektroskopisi, Hofmann-Tipi Klatratlar, 4-pridinkarboksialdehid, 1, 4-dioksan

Investigation of the FT-IR Spectroscopic Properties of M(4-Pyridinecarboxaldehyde)Ni(CN)4.nG Hofmann Type Clathrates (M = Ni, Cd and G = 1,4-Dioxane)

In this study, clathrate of 4-pyridinecarboxaldehyde tetracyanonickel-dioxane, given by the formula M(4-Pyridinecarboxaldehyde)Ni(CN)4 nG (m = Ni, Cd and G = 1,4-dioxane), is obtained for the first time through chemical methods. The FT-IR spectroscopic data in the region of (3000–400) cm-1 was recorded and the IR vibrational modes frequencies were given and explained in detail. The spectral analyzes results of the newly synthesized clathrate of 4-pyridinecarboxaldehyde tetracyanonickel- dioxane suggests that these clathrates are new examples of the Hofmann-type dioxane clathrates. In our study, the Hofmann-type dioxane clathrates formed by bounding electrons of nitrogen-donor atom of pyridine ring and electrons of oxygen-donor atom of aldehyde group (-CH=O) of 4-pyridinecarboxaldehyde ligand molecule to transition metal atoms consist of the corrugated |M–Ni(CN)4| polymeric layers which are held in parallel through the chain of (–M–4PCA–M–)

Keywords:

Kırmızıaltı Spektroskopisi, Hofmann-Tipi Klatratlar, 4-pridinkarboksialdehid, 4-dioksan,

PDF

___

Iwamoto T., Atwood J.L., Davies J.E.D., MacNicol D.D., 1984. Inclusion Compounds, vol. I, Academic Press, London, Chapter 2, p. 29
Graham Solomons T. W., 1996. Organic Chemistry, John Wiley & Sons, Inc. New York.
Iwamoto T, 1981. Recent developments in the chemistry of Hofmann-type and the analogous clathrates, Journal of Molecular Structure, 75 (1): 51-65.
http://www.wikipedia.org (10.04.2013)
Melnik M., Macaskova L., 1993. Structural aspects of red copper(I) compounds, Coordination Chemistry Reviews, 126(1-2): 71-92.
Sheeja Lovely K. L. P., Christudhas M. and Isac Sobana Raj C., 2012. The DNA cleavage and antimicrobial studies of Cu (II), Ni (II), Zn (II) and Co (II) complexes of 4- pyridine carboxaldehyde and Tryptophan, Journal of Chemical and Pharmaceutical Research, 4(11): 4762-4769.
Lu J.Y., Babb A.M., 2001. An unprecedented interpenetrating structure with two covalent-bonded open- framework of different dimensionality, Chemical Communications, (9): 821-822.
Karabatsos G.J., Vane F.M., 1963. Structural studies by nuclear magnetic resonance. Vİ. The stereospecificity of coupling between protons separated by five bonds and conformations of some aromatic aldehydes, Journal of American Chemical Society, 85(23): 3886-3888.
Lunazzi L., Macciantelli D., Cerioni G., 1976. Conformational studies by dynamic nuclear magnetic resonance. Part 4. Rotational isomers and torsional barriers of pyridinecarbaldehydes, Journal of Chemical Society, Perkin II, (15): 1791-1796.
Georgiou K., Roussy G., 1980. The microwave spectrum of 4-pyridinecarbaldehyde (isonicotinealdehyde) Journal of Molecular Spectroscopy, 82 (1): 176-184.
Sağlam A., Ucun F., Güçlü V., 2007. Molecular structures and vibrational frequencies of 2-, 3- and 4- pyridine carboxaldehydes by ab initio Hartree–Fock and density functional theory calculations, Spectrochimica Acta Part A, 67(2): 465-471.
Umar Y., 2009. Density functional theory calculations of the internal rotations and vibrational spectra of 2-, 3- and 4-formyl pyridine, Spectrochimica Acta Part A, 71 (4): 1907–1913.
Małecki J.G., Zwoliński P., 2012. Synthesis, characterization and molecular structure of Pd(II) complex containing the methyl-hemiacetal form of isonicotinaldehyde, Polyhedron 39 (1): 85-90.
Ataç A., Bardak F., 2006. Synthesis and Vibrational Spectroscopic Study of Some Metal(II) Halide and Tetracyanonickelate Complexes of Isonicotinic Acid, Turkish Journal of Chemistry, 30(5): 609-618.
Yurdakul S., Ataç A., Şahin E. and İde S., 2003. Synthesis, spectroscopic and structural studies on metal halide complexes of isonicotinamide, Vibrational Spectroscopy, 31 (1): 41-49.
Yurdakul S., Atac A., 2004. Fourier transform-infrared spectroscopic study of isonicotinamide metal(II) tetracyanonickelate and halide complexes, Spectroscopy Letters, 37(1): 33-42.
Nakamoto K., 1970. Infrared Spectra of Inorganic and Coordination Compounds, 2nd Edition, Wiley- Interscience, New York.
Can N., Ataç A., Bardak F. and Can S.E.S., 2005. Spectroscopic and luminescence properties of an isonicotinic acid, Turkish Journal of Chemistry, 29 (6): 589-595.
McCullough R.L., Jones L.H., Crosby G.A., 1960. An analysis of the vibrational spectrum of the tetracyanonickelate(II) ion in a crystal lattice, Spectrochimica Acta, 16(8): 929-944.
Kartal Z., Sayın E., 2011. FTIR spectroscopic and thermal study of M(Cyclohexanethiol)2Ni(CN)4·(1,4- dioxane) clathrate (M = Mn, Co, Ni and Cd), Journal of Molecular Structure 994 (1-3): 170-178.
Bellamy L.J., Branch R.F., 1954. The infra-red spectra of chelate compounds. Part II. Metal chelate compounds of β-diketones and of salicylaldehyde, Journal of the Chemical Society (Resumed), (0): 4491-4494.
Davies M., 1963. Infrared Spectroscopy and Molecular Structure, Elsevier, Amsterdam.
Chapman D. M., Hester R. E., 1997. Ab Initio Conformational Analysis of 1,4-Dioxane, The Journal of Physical Chemistry A, 101 (18) 3382–3387.
Ömer İlhan Karatepe e-posta: omerilhankaratepe@hotmail.com