The exciton chirality method (ECM) is commonly recognized as one of the best approaches to assign the absolute configuration of biaryls. This paper reports the first exception to this method for a simple biaryl system. ECD and VCD measurements in combination with DFT (B3LYP/6-311G∗), TDDFT (CAM-B3LYP/6-311G∗), and Coupled-Cluster (RI-SCS- CC2) calculations were used to determine the absolute configurations of axially chiral BODIPY DYEmers. The ECM fails to predict the sign of the intense CD couplet at 500 nm of the 1,1'-coupled dimer. The odd behavior was rationalized by considering the strong transition magnetic dipole associated with the 500 nm transition, which leads to an unexpected dominance of the mm coupling at the expense of the mm one in these compounds. This is the first case in which a strong electric magnetic coupling hampers the use of the ECM, but this behavior should not be restricted to the BODIPY chromophore.
Axially Chiral BODIPY DYEmers: An Apparent Exception to the Exciton Chirality Rule
PESCITELLI, GENNARO;JURINOVICH, SANDRO;
2014-01-01
Abstract
The exciton chirality method (ECM) is commonly recognized as one of the best approaches to assign the absolute configuration of biaryls. This paper reports the first exception to this method for a simple biaryl system. ECD and VCD measurements in combination with DFT (B3LYP/6-311G∗), TDDFT (CAM-B3LYP/6-311G∗), and Coupled-Cluster (RI-SCS- CC2) calculations were used to determine the absolute configurations of axially chiral BODIPY DYEmers. The ECM fails to predict the sign of the intense CD couplet at 500 nm of the 1,1'-coupled dimer. The odd behavior was rationalized by considering the strong transition magnetic dipole associated with the 500 nm transition, which leads to an unexpected dominance of the mm coupling at the expense of the mm one in these compounds. This is the first case in which a strong electric magnetic coupling hampers the use of the ECM, but this behavior should not be restricted to the BODIPY chromophore.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
