93673-00-8Relevant articles and documents
Synthesis, spectroscopy, electrochemistry, spectroelectrochemistry, Langmuir-Blodgett film formation, and molecular orbital calculations of planar binuclear phthalocyanines
Kobayashi, Nagao,Lam, Herman,Nevin, W. Andrew,Janda, Pavel,Leznoff, Clifford C.,Koyama, Toshiki,Monden, Atsushi,Shirai, Hirofusa
, p. 879 - 890 (1994)
A planar binuclear phthalocyanine and its dizinc and dicobalt derivatives, in which two phthalocyanine units share a common benzene ring, have been studied by spectroscopy, electrochemistry, and spectroelectrochemistry. Their Langmuir-Blodgett film-forming properties have been examined, and the results of molecular orbital calculations on these and related systems are also presented. The properties are compared with those of the corresponding mononuclear control molecules. UV-visible-near IR absorption and magnetic circular dichroism spectroscopies and cyclic and differential pulse voltammetry indicate that, in these compounds, two relatively independent chromophore units interact and therefore that the two phthalocyanine planes are not completely planar in solution. The electrochemical and spectroelectrochemical measurements show the formations of various mixed-valence oxidation and reduction species in the binuclear compounds. The nonmetalated and dizinc complexes exhibit both S1 and S2 emission. The radiative lifetimes (τ) of the dizinc complex are smaller than those of the metal-free binuclear derivative for both S1 and S2 emission, while the quantum yields (φF) are larger. Furthermore, for S2 emission, the φF and τ values of the binuclear compounds are larger than those of the corresponding mononuclear control molecules. Molecular orbital calculations within the framework of the Pariser-Parr-Pople approximation reproduce the splitting of the Q absorption band and further show that the splitting becomes larger the smaller the size of the shared common aromatic unit. In monolayers spread on water, the metal-free binuclear complex appears to have a slipped-stack conformation, tilted from the airwater interface normal plane. In Langmuir-Blodgett films, it may form a slipped-stack molecular arrangement with the stacking axis parallel to the substrate and/or a flat-lying conformation on the substrate surface.
Syntheses of Monometalated and Unsymmetrically Substituted Binuclear Phthalocyanines and a Pentanuclear Phthalocyanine by Solution and Polymer Support Methods
Leznoff, Clifford C.,Svirskaya, Polina I.,Khouw, Ben,Cerny, Ronald L.,Seymour, Penny,Lever, A. B. P.
, p. 82 - 90 (2007/10/02)
Binuclear phthalocyanines in which two different phthalocyanine nuclei are covalently linked through five-atom bridges, derived from 2-ethyl-2-methylpropane-1,3-diol, are prepared.In the examples, one phthalocyanine ring is always substituted with neopentyloxy substitutents, while the other phthalocyanine rin is unsubstituted or contains tert-butyl substituents or a neopentoxy-substituted copper phthalocyanine, constituting a binuclear phthalocyanine in which only one ring is metalated.The precursor, 2-(2-hydroxymethyl)-2-methylbutoxy)-9,16,23-trineopentoxyphthalocyanine was prepared in solution and also by solid-phase methods, using polymer-bound trityl chloride derived from a 1percent divinylbenzene-co-styrene copolymer.In some experiments some rare examples of demetalation of some zinc phthalocyanines are noted during phthalocyanine formation.A modified flash chromatography procedure proved to be useful for separating similarly substituted mononuclear phthalocyanines.
Preparation of Substituted Tetrabenzotriazaporphyrins and a Tetranaphthotriazaporphyrin: A Route to Mono-meso-substituted Phthalocyanine Analogues
Leznoff, Clifford C.,McKeown, Neil B.
, p. 2186 - 2190 (2007/10/02)
The synthesis, by treatment of phthalonitriles or 6-tert-butyl-2,3-dicyanonaphthalene with Grignard reagents, of novel substituted derivatives of tetrabenzotriazaporphyrins and a substituted tetranaphthotriazaporphyrin are described.Mono-meso-substituted tetrabenzotriazaporphyrins, soluble in organic compounds, were the major products, but byproducts of phthalocyanines and, in one case, tetrabenzodiazaporphyrins were obtained.
