Search

The synthesis, characterization, and electrochemical studies of [beta],[beta]'-fused metallocenoporphyrins are described. The novel Pd(0) catalyzed [3@] cycloaddition reaction with porphyrins was studied, a series of [beta][beta]' fused monoruthenoceno metalloporphyrins and bismetalloporphyrins with different central metals were prepared and significant electronic interactions between the metallocene and metalloporphyrin were observed.

Research has been conducted on nickel(II) porphyrins. The electrochemistry of these compounds has been investigated in the effort to understand the effect of structural and electronic factors on electron-transfer processes in porphyrins, and the details are reported.

The preparation and investigation of a novel trimeric porphyrin array with directly fused macrocycles via their beta-pyrrolic carbons, is described.

A study was conducted to examine the effects of the symmetry of substitution pattern and substituent orientations on the out-plane and in-plane distortions of the macrocyle of nickel porphyrins. These nickel porphyrins were analyzed through the use of molecular mechanics calculations, X-ray crystallography, UV visible absorption spectroscopy and resonance Raman spectroscopy. Results revealed that out-plane and in-plane distortions were dependent on perturbation symmetry of the peripheral substituents.

Research was conducted to study the influence of central metals of various sizes on the macrocyclic structure of a series of 5,15-disubstituted metallophorphyrins. Methodologies used included X-ray crystallography, resonance Raman spectroscopy and molecular mechanics. The contributions of the ruf and dom deformations in the crystal structures of several metal complexes of the phorphyrins were found to be metal-dependent. Results indicate the quantitative validity of normal-coordinate structural decomposition.

The synthesis and spectroscopic characterization of a series of porphyrins with ether-linked straps are presented. The biphenyl straps used were linked via their 3,3'-positions by SCH2O groups to orthopositions of the phenyl rings of the 5,15-diphenylporphyrins. The conformational properties and the electronic spectral properties of the strapped porphyrins were examined using 1H NMR spectroscopy. Also, the synthesis, structures and properties of ferrous carbonyl adducts of these porphyrins are presented and discussed.

Corrole is a tetraphrrolic macrocycle present in octamethylcorrole. It can stabilize higher oxidation states for coordinated metals and its molecular skeleton can maintain a planar conformation. The unusual reactivity of corrole in the Vilsmeier reaction is reported. Also a direct synthesis of formylcorroles by prefunctionalized a,c-biladiene salts is described.

The effect of substituents with increasing steric demands on the structure of nickel(II) 5,15-disubstituted porphyrins was studied by X-ray crystallography, UV-visible absorption spectroscopy, resonance Raman spectroscopy, molecular energy optimization computations and INDO/s molecular orbital computations. Findings showed that the distortion of the macrocyle for the disubstituted nickel porphyrins is a combination of ruffling and doming distortions. Also, the gal distortion can be precisely described in terms of displacements along the lowest-frequency normal coordinates of B1u and A2u symmetry.

Methods for the synthesis of biscorrole, porphyrin-corrole, bisporphyrin, bischlorin and porphyrin-chlorin heterodimers are presented. The development of the techniques for the synthesis of systems with the corrole nucleaus is particularly challenging since little is known about the synthetic chemistry of corrole. The synthesized products are characterized using a combination of nuclear magnetic resonance spectroscopy, ultraviolet spectrometry, mass spectroscopy and elemental analysis techniques.

The development and the application of a new catechol-based universal support for the synthesis of oligonucleotide are discussed. The support is found to be able to cleave and deprotect under mild conditions and hence is extremely effective.

Research has been conducted on aryl-porphyrin rotational barrier. The authors have used NMR spectroscopy in examining the relationship between this barrier and the core substituent M in some octaphenylporphyrins.

A synthesis of pyrroloporhyrins, involving reactions of metallo-2-nitro-5,10,15,20-tetraphenylporphyrin with isocyanoacetates, provided the required pyrroloporphyrin product, and a Zn(II) cyclopropylchlorin. A new methodology was developed to prepare dihydroporphyrins using a conjugate addition of carbon-centred nucleophiles to nitroalkenes. Carbon-carbon bonds can be selectively generated to prepare novel and highly functionalized chlorin systems through the reaction of active methylene complexes.