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Enhancing Selectivity and Kinetics in Oxidative Photocyclization by Supramolecular Control
Author(s) -
Haldar Ritesh,
Diring Stéphane,
Samanta Pralok K.,
Muth Marius,
Clancy William,
Mazel Antoine,
Schlabach Sabine,
Kirschhöfer Frank,
BrennerWeiß Gerald,
Pati Swapan K.,
Odobel Fabrice,
Wöll Christof
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201806996
Subject(s) - selectivity , chemistry , kinetics , supramolecular chemistry , photochemistry , stereocenter , chemical kinetics , catalysis , organic chemistry , molecule , enantioselective synthesis , physics , quantum mechanics
Abstract Photochemical reactions typically proceed via multiple reaction pathways, yielding a variety of isomers and products. Enhancing the selectivity is challenging. Now, the potential of supramolecular control for oxidative photocyclization of a tetraarylethylene, containing a stereogenic −C=C− bond, is demonstrated. In solution, this photochemical reaction produces three constitutional isomers (substituted phenanthrenes), with slow kinetics. When the reactant is assembled into a crystalline framework, only one product forms with accelerated kinetics. Key to this selectivity enhancement is the integration into a surface grown metal–organic framework (SURMOF); the dramatic gain in selectivity is ascribed to the hindrance of the rotational freedom of the −C=C− double bond. The structure of the MOF is key; the corresponding reaction in the solid does not result in such a high increase in selectivity. A striking change of luminescence properties after photocyclization is observed.