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Side Methyl Groups Control the Conformation and Contribute to Symmetry Breaking of Isoprenoid Chromophores
Author(s) -
Fiedor Leszek,
Pilch Mariusz
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.201802094
Subject(s) - chromophore , chemistry , conjugated system , chirality (physics) , polyene , circular dichroism , crystallography , porphyrin , stereochemistry , computational chemistry , photochemistry , symmetry breaking , chiral symmetry breaking , physics , organic chemistry , polymer , quantum mechanics , nambu–jona lasinio model
Ab initio DFT computations reveal that the essential structural and photophysical features of the conjugated π‐electron system of retinal and carotenoids are dictated by “innocent” methyl substituents. These methyl groups shape the conformation and symmetry of the isoprenoid chromophores by causing a sigmoidal distortion of the polyene skeleton and increasing its flexibility, which facilitates fitting to their binding pockets in proteins. Comparison of in vacuo conformations of the chromophores with their native (protein‐bound) conformations showed, surprisingly, that the peripheral groups and interactions with the protein environment are much less significant than the methyl side groups in tuning their structural features. The methyl side groups also contribute to a loss of symmetry elements specific to linear polyenes. In effect, the symmetry‐imposed restrictions on the chromophore electronic properties are disabled, which is of tremendous relevance to their photophysics. This is evidenced by their non‐negligible permanent dipole moments and by the simulated and experimentally measured circular dichroism spectra, which necessarily reflect the chirality of the conjugated π‐electron system.