ABSTRACT
A series of new bacteriochlorins was synthesized using 13(2)-oxo-bacteriopyropheophorbide a (derived from bacteriochlorophyll a) as a starting material, which on reacting with o-phenylenediamine and 1,10-diaminonaphthalene afforded highly conjugated annulated bacteriochlorins with fused quinoxaline, benzimidazole, and perimidine rings, respectively. The absorption spectra of these novel bacteriochlorins demonstrated remarkably red-shifted intense Q(y) absorption bands observed in the range of 816-850 nm with high molar extinction coefficients (89,900-136,800). Treatment of 13(2)-oxo-bacteriopyropheophorbide a methyl ester with diazomethane resulted in the formation of bacterioverdins containing a fused six-membered methoxy-substituted cyclohexenone (verdin) as an isomeric mixture. The pure isomers which exhibit long-wavelength absorptions in the near-IR region (865-890 nm) are highly stable at room temperature with high reactivity with O(2) at the triplet photoexcited state and favorable redox potential and could be potential candidates for use as photosensitizers in photodynamic therapy (PDT).
Subject(s)
Bacteriochlorophyll A/chemistry , Bacteriochlorophyll A/chemical synthesis , Porphyrins/chemistry , Porphyrins/chemical synthesis , Absorption , Electrochemistry , Molecular Structure , Photochemistry , Photochemotherapy , Photosensitizing Agents , Quantum Theory , Spectroscopy, Near-InfraredABSTRACT
[5,10,15,20-Tetrakis(4-n-propylamino-2,3,5,6- tetrafluorophenyl)porphyrinato]zinc(II) self-assembles into a two-dimensional supramolecular array in which each porphyrin is linked to four orthogonally-oriented chromophores.
Subject(s)
Metalloporphyrins/chemistry , Amines/chemistry , Fluorine , Models, Molecular , Molecular ConformationABSTRACT
The synthesis, characterization, and molecular structures of the first air-stable, hexacoordinated high spin Fe(II) porphyrins (1) with axial alcohols are reported (1 = Fe(II) meso-tetrakis(o-dichlorophenyl)-beta-octanitroporphyrin). The structure of 1 with two axial waters is also presented. The very different conformations and metrics observed with the two types of ligands illustrate the acute interplay between ligands, conformations, and spin states in Fe porphyrins.