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Lukyanets E.A.,Organic Intermediates and Dyes Institute | Nemykin V.N.,University of Minnesota
Journal of Porphyrins and Phthalocyanines | Year: 2010

The preparation and optical properties of peripherally substituted phthalocyanines and their analogs (i.e. naphthalocyanines, anthracyanines, aza-analogs of phthalocyanines, and tetraazaporphyrins) have been widely discussed. This review highlights methodologies that have been published in poorly known and mostly unavailable Russian journals. © 2010 World Scientific Publishing Company. Source

Solntsev P.V.,University of Minnesota | Dudkin S.V.,University of Minnesota | Dudkin S.V.,Organic Intermediates and Dyes Institute | Sabin J.R.,University of Minnesota | Nemykin V.N.,University of Minnesota
Organometallics | Year: 2011

Orange dimethyl (Z)-2,3-bis(ferrocenyl)-2-butenedioate (1) and blue (Z)-2,3-bis(ferrocenyl)maleimide (2) were prepared and characterized using NMR, IR, and UV-vis spectroscopy as well as X-ray crystallography. X-ray crystallographic studies of 1 and 2 revealed a locked anti conformation of the ferrocene substituents, which was explained on the basis of the steric properties of these groups. Electronic structures and solvatochromic properties of 1 and 2 were investigated by UV-vis spectroscopy and polarized continuum model (PCM) density functional theory (DFTPCM) as well as time-dependent DFT (TDDFT-PCM) approaches. The calculated vertical excitation energies are consistent with the experimental data and clearly suggest the dominance of metal-to-ligand charge-transfer bands in the visible region of the UV-vis spectra for 1 and 2. Redox properties of 1 and 2 were investigated using cyclic voltammetry, differential pulse voltammetry, and spectroelectrochemical and chemical oxidation approaches. In aDCM/(NBu4)[B(C6F 5)4] system, ferrocene-centered oxidation processes in 1 and 2 are separated by 300 and 345 mV, respectively. Stepwise chemical and spectroelectrochemical oxidation of 1 and 2 allowed us to obtain spectroscopic signatures of the mixed-valence 1+ and 2+ cations. Hush analysis of the intervalence charge-transfer bands in 1+ and 2 + is suggestive of class II (in Robin and Day classification) behavior. © 2011 American Chemical Society. Source

Nemykina V.N.,University of Minnesota | Lukyanets E.A.,Organic Intermediates and Dyes Institute
Arkivoc | Year: 2010

This review summarizes the synthetic strategies for substituted phthalonitriles and phthalocyanines. Preparation of alkyl-, aryl-, halo-, nitro-, alkoxy-, aryloxy-, alkylthio-, arylthio-, and amino- substituted phthalocyanines along with the derivatives of phthalocyanine carboxylicand sulfoacids is overviewed. Influence of the substituents on the position of Q-band in UV-vis spectra of substituted phthalocyanines is also briefly discussed. Source

Matsushita O.,Tohoku University | Derkacheva V.M.,Organic Intermediates and Dyes Institute | Muranaka A.,RIKEN | Muranaka A.,Japan Science and Technology Agency | And 5 more authors.
Journal of the American Chemical Society | Year: 2012

Expanded phthalocyanine (Pc) congeners with two Mo or W central metal ions and four isoindole ring moieties have been synthesized using normal Pc formation conditions in the presence of urea. The products have been characterized by electrochemistry; mass spectrometry (MS); IR, electron paramagnetic resonance (EPR), NMR, electronic absorption, and magnetic circular dichroism (MCD) spectroscopies; and X-ray analysis. The X-ray structures have rectangular C 2v symmetry and provide evidence that the central Mo atoms are linked by a single bond and coordinated by two isoindole nitrogen atoms and two nitrogen atoms from the amine moieties. The electronic absorption bands extend into the 1200-1500 nm region. This can be explained using Gouterman's four-orbital theory. The experimental NMR data and theoretical calculations provide evidence for a heteroaromatic 22-π-electron conjugation system for the ring-expanded Pc system, which satisfies Hückel's (4n + 2)π aromaticity. © 2012 American Chemical Society. Source

Nemykin V.N.,University of Minnesota | Polshyna A.E.,University of Minnesota | Makarova E.A.,University of Minnesota | Makarova E.A.,Organic Intermediates and Dyes Institute | And 2 more authors.
Chemical Communications | Year: 2012

Minor products in the reaction between substituted 1,3-diiminoisoindolines and 2,5-diamino-3,4-dicyanothiophene were identified as the nickel seco-tribenzoporphyrazines 4 and 5, which have been characterized by UV-vis, MCD, NMR, and mass spectroscopy. Experimentally observed tetraazachlorin-type UV-vis spectra of new seco-tribenzoporphyrazines were explained on the basis of DFT and TDDFT calculations. © 2012 The Royal Society of Chemistry. Source

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