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2,7,12,17‐Tetra( p ‐butylphenyl)‐3,6,13,16‐tetraazaporphycene: The First Example of a Straightforward Synthetic Approach to a New Class of Photosensitizing Macrocycles
Author(s) -
ll Santi,
Borrell José I.,
Borrós Salvador,
Colominas Carles,
Rey Oscar,
Rubio Noemí,
SánchezGarcía David,
Teixidó Jordi
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200200684
Subject(s) - bathochromic shift , chemistry , aromatization , tetra , substituent , yield (engineering) , stereochemistry , suzuki reaction , oxidative coupling of methane , combinatorial chemistry , medicinal chemistry , organic chemistry , catalysis , palladium , physics , materials science , quantum mechanics , metallurgy , fluorescence
Selected on the basis of computational studies and synthetic feasibility, the title compound 9c has been obtained by cross‐coupling of 4,4′‐bis( p ‐butylphenyl)‐2,2′‐biimidazole‐5,5′‐dicarbaldehyde ( 28c ) followed by oxidative aromatization. The introduction of a Suzuki coupling protocol opens the way to 2,7,12,17‐tetraryl‐substituted 3,6,13,16‐tetraazaporphycenes avoiding the development of a de novo synthesis whenever a new peripheral substituent is desired. As predicted by computational studies, oxidation of the non‐aromatic precursor 33c to yield the azaporphycene macrocycle 9c is more favourable than in the case of porphycene itself. The absorption spectrum of 9c shows a substantial bathochromic shift relative to porphycene 1a , revealing a synergism between aza substitution in the macrocycle and phenyl substitution at its periphery. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)