Abstract
A new vic-dioxime ligand, N,N′-bis(aminopyreneglyoxime) (LH2), and its copper(II), nickel(II) and cobalt(II) metal complexes were synthesized and characterized by elemental analyses, IR, UVVIS and 1H and 13C NMR spectra (for the ligand). Mononuclear complexes were synthesized by a reaction of ligand (LH2) and salts of Co(II), Ni(II), and Cu(II) in ethanol. The complexes have the metal-ligand ratio of 1: 2 and metals are coordinated by N,N′ atoms of vicinal dioximes. The ligand acts in a polydentate fashion bending through nitrogen atoms in the presence of a base, as do most vic-dioximes. Detection of a H-bonding in the Co(II), Ni(II), and Cu(II) complexes by IR revealed the square-planar MN4 coordination of mononuclear complexes. Fluorescent properties of the ligand and its complexes arise from pyrene units conjugated with a vic-dioxime moiety. Fluorescence emission spectra of the ligand showed a drastic decrease in its fluorescence intensity upon metal binding. The electrochemical properties of the complexes were studied by the cyclic voltammetry technique. The nickel complex displayed an irreversible oxidation process while the copper complex exhibited a quasi-reversible oxidation and reduction processes based on the copper Cu(II)/Cu(III) and Cu(II)/Cu(I) couples, respectively.
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Ali, S. A., Soliman, A. A., Aboaly, M. M., & Ramadan, R. M. (2002). Chromium, molybdenum and ruthenium complexes of 2-hydroxyacetophenone Schiff bases. Journal of Coordination Chemistry, 55, 1161–1170. DOI: 10.1080/0095897021000023509.
Amann, N., Pandurski, E., Fiebig, T., & Wagenknecht, H. A. (2002). A model nucleoside for electron injection into DNA: 5-pyrenyl-2′-deoxyribose. Angewandte Chemie International Edition, 41, 2978–2980. DOI: 10.1002/1521-3773(20020816)41:16〈2978::AID-ANIE2978〉3.0.CO;2-5.
Bard, A. J., & Faulkner, L. R. (Eds.) (2001). Electrochemical methods: Fundamentals and applications (2nd ed.). New York: John Wiley & Sons.
Boyer, J. H. (1980). Increasing the index of covalent oxygen bonding at nitrogen attached to carbon. Chemical Reviews, 80, 495–561. DOI: 10.1021/cr60328a002.
Chakravorty, A. (1974). Structural chemistry of transition metals complexes of oximes. Coordination Chemical Reviews, 13, 1–46. DOI: 10.1016/S0010-8545(00)80250-7.
Cotton, F. A., & Wilkinson, G. (1988). Advanced Inorganic Chemistry (5th ed.). New York: John Wiley & Sons. (pp. 725–743).
Gelir, A., Yilmaz, I., & Yilmaz, Y. (2007). In situ monitoring of the synthesis of a pyranine-substituted phthalonitrile derivative via the steady-state fluorescence technique. Journal of Physical Chemistry B, 111, 478–484. DOI: 10.1021/jp064462w.
Grabowski, Z. R., Rotkiewicz, K., & Rettig, W. (2003). Structural changes accompanying intramolecular electron transfer: Focus on twisted intramolecular charge-transfer states and structures. Chemical Reviews, 103, 3899–4031. DOI: 10.1021/cr940745l.
Kilic, A., Tas, E., Gumgum, B., & Yilmaz, I. (2006a). Synthesis, spectral characterization and electrochemical properties of new vic-dioxime complexes bearing carboxylate. Transition Metal Chemistry, 31, 645–652. DOI: 10.1007/s11243-006-0043-z.
Kilic, A., Tas, E., Gumgum, B., & Yilmaz, I. (2006b). Synthesis, spectroscopic and electrochemical investigations of two vic-dioximes and their mononuclear Ni(II), Cu(II) and Co(II) metal complexes containing morpholine group. Chinese Journal of Chemistry, 24, 1599–1604. DOI: 10.1002/cjoc.200690 299.
Kilic, A., Tas, E., Gumgum, B., & Yilmaz, I. (2007a). The synthesis, spectroscopic and voltametric studies of new metal complexes containing three different vic-dioximes. Journal of Coordination Chemistry, 60, 1233–1246. DOI: 10.1080/00958970601035914.
Kilic, A., Tas, E., Gumgum, B., & Yilmaz, I. (2007b). Three new vic-dioxime ligands: synthesis, characterization, spectroscopy, and redox properties of their mononuclear nickel(II) complexes. Heteroatom Chemistry, 18, 657–663. DOI: 10.1002/hc
Krasnansky, R., & Thomas, J. K. (1994). Aminopyrene as a monitor of vicinal and geminal OH groups on silica. Langmuir, 10, 4551–4553. DOI: 10.1021/la00024a027.
Kumar, K. N., & Ramesh, R. (2005). Synthesis, luminescent, redox and catalytic properties of Ru(II) carbonyl complexes containing 2N2O donors. Polyhedron, 24, 1885–1892. DOI: 10.1016/j.poly.2005.05.020.
Lakowicz, J. R. (1983). Principle of fluorescence spectroscopy. New York: Plenum Press.
Li, L., & Mohwald, H. (2004). Photoinduced vectorial charge transfer across walls of hollow microcapsules. Angewandte Chemie International Edition, 43, 360–363. DOI: 10.1002/anie.200352657.
Oguchi, K., Sanui, K., Ogata, N., Takahashi, Y., & Nakada, T. (1990). Relationship between electron sensitivity and chemical structures of polymers as electron-beam resist. 7. electron sensitivity of vinyl-polymers containing pendant 1,3-dioxolan groups. Polymer Engineering and Science, 30, 449–452. DOI: 0.1002/pen.760300804.
Ozkaya, A. R., Okur, A. I., Gül, A., & Bekaroglu, Ö. (1994). Electrochemical studies of tetracrown-ether substituted phthalocyanines in solution. Journal of Coordination Chemistry, 33, 311–318. DOI: 10.1080/00958979408024291.
Ozkaya, A. R., Yilmaz, I., & Bekaroglu, Ö. (1998). Electrochemical and adsorption properties of novel phthalocyanines with four 16-membered diazadithia macrocycles. Journal of Porphyrins and Phthalocyanines. 2, 483–492. DOI: 10.1002/(SICI)1099-1409(199811/12)2:6〈483::AID-JPP79〉3.0.CO;2-Z.
Pereira, R. V., & Gehlen, M. H. (2006). H-bonding assisted intramolecular charge transfer in 1-aminopyrene derivatives. Chemical Physics Letters, 426, 311–317. DOI: 10.1016/j.cplett.2006.05.109.
Schrauzer, G. N., & Kohnle, J. (1964). Coenzym B12-Modelle. Chemische Berichte, 97, 3056–3064. DOI: 10.1002/cber.19640971114.
Singh, R. B., Garg, B. S., & Singh, R. P. (1979). Oximes as spectrophotometric reagents—a review. Talanta, 26, 425–444. DOI: 10.1016/0039-9140(79)80107-1.
Smith, P. A. S. (1966). The chemistry of open-chain organic nitrogen compounds (vol. 2). New York: W. A. Benjamin.
Sumalekshmy, S., & Gopidas, K. R. (2004). Photoinduced intramolecular charge transfer in donor-acceptor substituted tetrahydropyrenes. Journal of Physical Chemistry B, 108, 3705–3712. DOI: 10.1021/jp036043u.
Tas, E., Aslanoglu, M., Kilic, A., & Kara, Z. (2005). Synthesis, characterization and redox properties of three new vic-dioximes and their nickel(II) metal complexes. Transition Metal Chemistry, 30, 758–764. DOI: 10.1007/s11243-005-6226-1.
Tas, E., Aslanoglu, M., Kilic, A., & Kara, Z. (2006). Synthesis, spectroscopic and electrochemical studies of copper (II) and cobalt (II) complexes of three unsymmetrıcal vic-dioximes ligands. Journal of Coordination Chemistry, 59, 861–872. DOI: 10.1080/00958970500412206.
Tas, E., Ulusoy, M., Guler, M., & Yilmaz, I. (2004). Synthesis, characterization and redox properties of a new vic-dioxime and its transition metal complexes. Transition Metal Chemistry, 29, 180–184. DOI: 10.1023/B:TMCH.0000019417.35877.b9.
Thomas, T. W., & Underhill, A. E. (1972). Metal-metal interactions in transition-metal complexes containing infinite chains of metal atoms. Chemical Society Reviews, 1, 99–120. DOI: 10.1039/CS9720100099.
Tschugaeff, L. (1905). Über ein neues, empfindliches Reagens auf Nickel. Chemische Berichte, 38, 2520–2522. DOI: 10.1002/cber.19050380317.
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Yilmaz, I., Kilic, A. & Yalcinkaya, H. Synthesis, characterization, fluorescence and redox features of new vic-dioxime ligand bearing pyrene and its metal complexes. Chem. Pap. 62, 398–403 (2008). https://doi.org/10.2478/s11696-008-0046-7
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DOI: https://doi.org/10.2478/s11696-008-0046-7