CONTENTS

Pyridyl-substituted porphyrins bearing a reactive functionality were prepared via Suzuki cross-coupling reactions in very good yields. These compounds are precursors of new porphyrin architectures able to coordinate two metals: one in the porphyrin core and the second around the pyridyl moiety. During the coupling reactions, a higher reactivity of a chloro picolyl group was evidenced compared to a bromo function on the same reacting molecule.

The azoporphyrin dimer from nickel(II) 5,10-diarylporphyrin ("corner porphyrin") has been prepared and characterized by X-ray crystallography and spectroscopy. Some substitution reactions have been carried out. The zinc analogs did not yield the corresponding dizinc azoporphyrin.

A new series of 1,8(11),15(18),22(25)-tetraglycosylated zinc(II) phthalocyanines (PcZns) were synthesized using hexamethyldisilazane (HMDS), trimethylsilyltriflate (TMSOTf) and zinc salt in DMF to form the corresponding acetyl-protected PcZns, followed by deprotection of acetyl groups by NaOMe in methanol/DMSO mixture.

Visible light photostability of four water soluble tetrasubstituted phthalocyanines (SO₃H and COOH) of Pt and Ru were studied. All Ru derivatives were degraded without evidence for ¹O₂ generation. Among the investigated complexes, Pt tetrasulphophthalocyanine in neutral conditions showed a very good photostability with a concomitant production of ¹O₂, potentially usable for PDT or synthetic purpose.

Using reductive demetalation of Mn[Br₈TPFPC], we have synthesized β-octabromo-meso-tris(pentafluorophenyl)corrole, H₃[Br₈TPFPC], in free-base form for the first time.

The structure of floating layers of copper tetra-tert-butylphthalocyanine (CuPctBu4) and copper tetrabenzotriazaporphyrine is determined by a quantitative analysis of compression isotherms (with the use of Volmer equation) and by Brewster angle microscopy. The quantitative model of floating layer of copper tetra-tert-butylphthalocyanine is proposed. Constants characterizing a stable monolayer, as well as the region where it may be formed, are determined on the base of the model created.

Several oxacalix[4]arene-linked cofacial bisporphyrins have been synthesized, as free-bases, biszinc(II) and biscopper(II) complexes. Spectroscopic and electrochemical properties of these complexes were investigated. The enhanced electronic communications were observed in the biscopper(II) complex, which is consistent to the shorter Cu-Cu distance observed in compound 4 based on the HF/CEP-31G calculated results.

Tetrapyrazinoporphyrazine magnesium complexes and metal free compounds with four long, linear alkyl groups and four 4-tert-butyl phenyl groups at the peripheral positions were synthesized. The resulting chromophores contained alkyl chains substituted at their peripheries and showed good solubility in organic solvents. The fluorescence of the tetrapyrazinoporphyrazine magnesium complexes was greatly influenced by the intermolecular aggregation. Synthesized compounds were characterized by UV-visible spectroscopy, MALDI-TOF-MS (matrix-assisted laser desorption ionization time-of-flight mass) spectroscopy and ¹H NMR spectroscopy.

Meso-tetrakis(p-sulfonatophenyl)porphyrin functionalized Pt nanocomposite containing an organic photoreceptive shell and a Pt nanocore is active for water splitting to produce hydrogen in the absence of an electron relay.

A folate receptor mediated tumor targeting photosensitizer has been designed and synthesized. The folate receptor positive tumor cellular selective uptake and the photocytotoxicity in vitro of conjugate 1 have been evaluated.