Premium
Revisiting the Ullman's Radical Chemistry for Phthalocyanine Derivatives
Author(s) -
Fidan Ismail,
Luneau Dominique,
Ahsen Vefa,
Hirel Catherine
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201704903
Subject(s) - phthalocyanine , chemistry , solubility , electron paramagnetic resonance , context (archaeology) , photochemistry , nitroxide mediated radical polymerization , phthalonitrile , nitroxyl , organic chemistry , polymer , nuclear magnetic resonance , polymerization , radical polymerization , paleontology , physics , biology
Phthalocyanine derivatives do not cease to gain attention due to their numerous properties and applications (e.g., sensor, PDT). This makes them a unique scaffold for the design of new material. In this context, we were interested to develop the synthesis of an imino nitroxide‐substituted phthalocyanine by Ullman's procedure; a challenge due to the intrinsic low solubility of most phthalocyanine derivative in much solvents. To overcome this solubility problem, we designed a phthalocyanine with bulky neopentyl substituents in peripheral positions as counterpart to the imino nitroxide moieties. The imino nitroxide‐substituted phthalocyanine was obtained by condensation of a monoformyl‐substituted phthalocyanine with 2,3‐bis(hydroxylamino)‐2,3‐dimethylbutane in refluxing THF–MeOH (2:1) mixture in the presence of p ‐toluenesulfonic acid monohydrate, follow by oxidation with PbO 2 . Characterization was performed by electrochemistry, UV/Vis and EPR spectroscopy in solution as well as SQUID in solid state.