Photoinduced Intramolecular Charge Transfer Reaction in (E)-3-(4-Methylamino-phenyl)-acrylic Acid Methyl Ester:  A Fluorescence Study in Combination with TDDFT Calculation

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 110; no. 44; pp. 12089 - 12095
• Main Authors: Chakraborty, Amrita, Kar, Samiran, Nath, D. N, Guchhait, Nikhil
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.11.2006
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0629846

A donor−acceptor substituted aromatic system (E)-3-(4-Methylamino-phenyl)-acrylic acid methyl ester (MAPAME) has been synthesized, and its photophysical behavior obtained spectroscopically has been compared with the theoretical results. The observed dual fluorescence from MAPAME has been assigned to emission from locally excited and twisted intramolecular charge transfer states. The donor and acceptor angular dependency on the ground and excited states potential energy surfaces have been calculated both in vacuo and in acetonitrile solvent using time dependent density functional theory (TDDFT) and TDDFT polarized continuum model (TDDFT-PCM), respectively. Calculation predicts that a stabilized twisted excited state is responsible for red shifted charge transfer emission.