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Conformational Analysis and Binding Properties of a Cavity Containing Porphyrin Catalyst Provided with Urea Functions
Author(s) -
Hidalgo Ramos Pilar,
Saisaha Pattama,
Elemans Johannes A. A. W.,
Rowan Alan E.,
Nolte Roeland J. M.
Publication year - 2016
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.201600627
Subject(s) - porphyrin , chemistry , supramolecular chemistry , moiety , intramolecular force , supramolecular catalysis , catalysis , combinatorial chemistry , fluorescence spectroscopy , rotaxane , stereochemistry , photochemistry , polymer chemistry , fluorescence , organic chemistry , molecule , physics , quantum mechanics
Urea‐functionalized porphyrin catalysts containing a cavity, which are used for the processive epoxidation of polymers, are thoroughly characterized and their binding properties and other supramolecular features disclosed. Intramolecular coordination of the urea side chains to the metal center of the porphyrin moiety is unveiled through NMR, IR, UV, and fluorescence spectroscopy studies. This intramolecular coordination appears to be essential in order to facilitate catalysis in a pseudo‐rotaxane fashion, i.e. by preventing the use of an excess of bulky axial ligands. The current investigation provides information on how to modulate in a dynamic fashion the catalytic activity of supramolecular systems, which is of interest for the design of increasingly efficient processive catalysts.