Phthalocyanine complexes, theoretical studies

The redox potentials of zinc-substituted phthalocyanines are shown to be linearly dependent on the total Hammett substituent constant.837 In 1987, Stillman and co-workers used the absorption and magnetic circular dichroism spectra of the zinc phthalocyanine and its 7r-cation-radical species to assign the observed bands on the basis of theoretical calculations. The neutral and oxidized zinc phthalocyanine complexes with cyanide, imidazole, and pyridine were used with the key factor in these studies the stability of the 7r-cation-radical species.838 The structure of zinc chloro(phthalocyaninato) has been determined and conductivity investigated.839... 

Haber process, 116 Hafnium complexes alkyl alkoxy reactions, 358 phthalocyanines, 865 porphyrins, 823 pseudohalides, 228 Hafnium(IV) complexes cupferron, 512 Haloarsine compounds, 1004 Halogen complexes, 675-687 bridge systems, 677-684 asymmetry, 678 theoretical studies, 682 double bridged, 681... 

Synthetic, spectroscopic, and theoretical study of novel supramolecular structures composed of lanthanide phthalocyanine double-decker complexes 02CCR (226)93. 

The oxidation of 1-decene in aqueous DMF with catalytic amounts of Pd(OAc)2, hydroquinone and iron phthalocyanine was also studied (Fig. 3.). In the case of the free complex, after a relatively fast induction period (about 30 minutes), the reaction showed a linear uptake of oxygen, close to the consumption of the theoretical amount. The rate was similar to the literature value reported by BSckvall and coworkers [5]. 

The phthalocyanines, naphthalocyanines, and certain of their metal derivatives (Figure 6.17) are infrared fluorophores. 61"64 As a class, they are exceptionally stable compounds, with copper (Cu) phthalocyanine (not a fluorophore) remaining intact above 300 °C in air. First used for textile dyeing in the last century and still widely used, there is a rich chemistry of phthalocyanines. Most derivatives can be made by prolonged heating of a phthalimide or phthalic acid derivative with a metal in powder or salt form at elevated temperature. Several derivatives absorb in the near-IR, and either fluoresce or phosphoresce. The electronic transitions of phthalocyanines are complex and have been extensively studied, at least in part because the symmetry of the molecule makes theoretical calculations of its spectroscopic behavior more tractable. Unsubstituted phthalocyanines and naphthalocyanines are, as a class, very insoluble in solvents other than, for instance, nitrobenzene. Sulfonated phthalocyanines are water soluble and exhibit spectra comparable to the parent derivative. Photolumines-cent phthalocyanines (Pcs) include SiPc, ZnPc, and PC itself. These compounds have been little used for practical infrared fluorometry to date however, Diatron Corpora-... 

Moreover, supra-molecular systems involving crown ethers, fullerene and k-extended systems have been achieved that can mimic the photosynthetic process [9-14]. The fullerene Qo has been used successfully as an electron acceptor in the construction of model photosynthetic systems [9], the r-extended systems, such as porphyrins [12], phthalocyanines [13], r-extended tetrathiafulvalene (w -exTTF) derivatives [9,10], which are utilized as electron donors, while the crown ethers act as a bridge between the electron donor and acceptor. In the absorption spectrum of the complexes, the absorption maxima are associated experimentally and theoretically with the formation of charge-transfer states [14-16]. Consequently, these supramolecular systems have potential for applications in photonic, photocatalytic, and molecular optoelectronic gates and devices [9-14]. As a result, the study of the conformations and the complexation behavior of crown ethers and their derivatives are motivated both by scientific curiosity regarding the specificity of their binding and by potential technological applications. 

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