Spectral and Electrochemical Characterization of Dibenzotetraaza[14]annulenes

The UV/Vis absorption spectra and cyclic voltammograms (CV) of the Cu(II) and Ni(II) complexes of γ,γ'-alkoxycarbonyl derivatives of α,α'- diphenyldibenzo-tetraaza[14]annulene are analyzed and compared. The observed ratio of absorption intensities at the peaks of π-π* transitions is linearly correlated with the difference of HOMO and LUMO energy levels of the substituents. Moreover, the measured values of the mid-peak potential of metal redox reactions on a Pt electrode in DMF are linearly correlated with the ionization potential values of the appropriate substituents.

[1]  Ł. Dobrzycki,et al.  New alkoxycarbonyl derivatives of dibenzotetraaza[14]annulene. Crystal and molecular structure of [5,14-dihydro-7,16-diisopropoxycarbonyl-8,15-dimethyl-6,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinato(2-)-κ4N]nickel(II) , 2003 .

[2]  K. Woźniak,et al.  New chiral receptors based on dibenzotetraaza(14)annulenes , 2001 .

[3]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[4]  G. Friedermann,et al.  Semiempirical calculations on the redox potentials and electronic absorption spectrum of tetraazaannulenes , 2001 .

[6]  K. Woźniak,et al.  Synthesis, Structure and Binding Properties of Nickel and Copper [14]Cyclidene Complexes with Appended Aza Crown Ethers , 2004 .

[7]  R. D. Bereman,et al.  Electrochemical and spectral properties of the Ni(II) and Cu(II) complexes of 5,7,12,14-tetraphenyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene , 1989 .

[8]  K. Kadish,et al.  Solvent and substituent effects on the redox reactions of para-substituted tetraphenylporphyrin. , 1976, Journal of the American Chemical Society.

[9]  Jean-Michel Kerbaol,et al.  Cobalt(II)–dibenzotetraaza[14]annulene complex electropolymerization for electrode modification , 2000 .

[10]  Pankaj Kumar,et al.  New nickel(II) selective potentiometric sensor based on 5,7,12,14-tetramethyldibenzotetraazaannulene in a poly(vinyl chloride) matrix , 2000 .

[11]  R. D. Bereman,et al.  Electrochemical polymerization at an electrode surface: Film formation of the Ni(II) complex of dibenzo [b,i] [1,4,8,11]tetraaza[14]annulene and the Ni(II) and Cu(II) complexes of 5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene: Copolymerization and layered polymerization , 1990 .

[12]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[13]  J. Nørskov,et al.  Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals , 1999 .

[14]  F. Walker,et al.  Electronic effects in transition metal porphyrins. 2. The sensitivity of redox and ligand addition reactions in para-substituted tetraphenylporphyrin complexes of cobalt (II). , 1976, Journal of the American Chemical Society.