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The First Synthesis and Electronic Properties of Tetrakis[(hetero)phenanthrenyl]methanes
Author(s) -
Zimmermann Thomas J.,
Müller Thomas J. J.
Publication year - 2002
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 - 10.1002/1099-0690(200207)2002:14<2269::aid-ejoc2269>3.0.co;2-e
Subject(s) - chemistry , bathochromic shift , cyclic voltammetry , intramolecular force , photochemistry , aryl , oxidative coupling of methane , chromophore , heck reaction , absorption spectroscopy , medicinal chemistry , fluorescence , methane , stereochemistry , organic chemistry , electrochemistry , alkyl , physics , electrode , quantum mechanics
The tetrakis[(hetero)phenanthryl]methanes 9 have been synthesized from tetrakis( p ‐iodophenyl)methane ( 1 ) in a two‐step sequence consisting of a Heck aryl vinylation to give the tetrakis[β‐(aryl)‐ p ‐styryl]methanes 3 and subsequent oxidative photocyclization. The absorption and emission spectra of the stilbene derivatives 3 showed significant electronic coupling of the four branches both in the ground and in the excited states. According to cyclic voltammetry, the electron‐rich dimethylamino ( 3c ) and the electroneutral thienyl systems ( 3d ) displayed a rapid, cooperative oxidative fragmentation that could be partially suppressed at high scan rates. In the ferrocenyl systems ( 3g ), the organometallic fragments were oxidized simultaneously without notable mutual electronic communication. For the tetrakis[(hetero)phenanthryl]methanes 9 , both UV/Vis and fluorescence spectroscopy showed significant bathochromic shifts as a consequence of pronounced intramolecular coupling between the four chromophores. In a multicycle cyclic voltammetry experiment, the naphthothienyl derivative 9c was electropolymerized to give a thin, multicolored, transparent film on the anode. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)