Investigation of the ionization of phthalocyanines by luminescence spectra

On the basis of absorption and luminescence spectra and polarization measurements on phthalocyanine solutions in acid medium, it has been established that successive protonation probably occurs at the bridge nitrogen atoms; the protonated forms are asymmetric in acid medium.     

Composition and Structure of [WCl4{N(Et)C(O)}3Cl]: MALDI-TOF Mass Spectrometric Study

The product of introduction of three ethyl isocyanate molecules at the tungsten-chlorine bond, namely, [WCl₄{N(Et)C(O)}₃Cl], was synthesized via thermolysis of tungsten hexachloride with a threefold excess of ethyl isocyanate in dichloroethane and studied by MALDI-TOF mass spectrometry method. In addition to the peak of the molecular ion WCl₄{N(Et)C(O)}₃Cl]^- at 573.9 m/z, the mass spectrum of the complex exhibited the maxima at 342.0, 231.0, and 801.0 m/z assigned to [WOCl₄]^-, [{N(Et)C(O)}₃ · H₂O]⁺, and [WOCl₄{N(Et)C(O)}₆Cl]^-, respectively. These three ions can only form in the hydrolysis of the complex containing a chain ligand.     

Cationoid rearrangements in reactions of perfluoro-1-arylbenzocyclobutenes with antimony pentafluoride

In the presence of antimony pentafluoride at 130 °C, the four-membered ring of perfluoro-1-(2-ethylphenyl)benzocyclobutene (2) undergoes cleavage, forming perfluoro-2-ethyl-2′-methyldiphenylmethane (5). Compound 5 is converted, under the action of SbF₅ at 170 °C, to perfluoro-8,9-dimethyl-1,2,3,4-tetrahydrofluorene (8). Perfluoro-1-(4-ethylphenyl)benzocyclobutene (3) remains unchanged at 130 °C, whereas at 170 °C it gives a mixture of perfluorinated 4′-ethyl-2-methyldiphenylmethane (9), 6-ethyl-1,2,3,4-tetrahydroanthracene (11) and 2-ethyl-9,10-dihydroanthracene (12). When heated with SbF₅ at 170 °C, perfluoro-1-phenylbenzocyclobutene (1) remains unchanged. Solution of compounds 2, 3, 5 and 9 in SbF₅-SO₂ClF generated the perfluorinated 1-(2-ethylphenyl)-1-benzocyclobutenyl (29), 1-(4-ethylphenyl)-1-benzocyclobutenyl (30), 2-ethyl-2′-methyldiphenylmethyl (31) and 4′-ethyl-2-methyldiphenylmethyl (32) cations, respectively.     

Characteristic features of excess charge localization in stepwise three-electron reduction of Ni-octaethylporphin

We have investigated the electronic structure of Ni-octaethylporphin anions (NiOEP) by¹H NMR. We have established that in (NiOEP)–, the excess electron is localized in the orbital of the nickel, while the second and third extra electrons in (NiOEP)^2- and (NiOEP)^3- are localized in the orbitals of the ligand. We conclude that spin density is transferred between the d orbitals of the Ni and the orbitals of the porphyrin ligand.Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70 Prospekt Frantsiska Skoriny, Minsk 220072, Belarus. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 6, pp. 345–347, November–December, 1996. Original article submitted February 22, 1996.