title: Photoinduced charge transfer in solvated anthraquinones is facilitated by low-frequency ring deformations.
abstract: Efficiency of photoinduced charge transfer (CT) reactions in supramolecular assemblies is often compromised due to the rigid parametrization of acceptable donor-acceptor (D-A) distances and orientations. Using a combined approach of time-resolved optical measurements and electronic structure studies guided by molecular dynamics (MD) simulations, we demonstrate that dynamic control on CT rate exists for quenching of hydroxy-anthraquinones in donor aniline-like solvents. We find that anthraquinone ring deformation modes control the kinetics of CT within ∼300-700 fs by modulating the D-A electronic couplings. Our work demonstrates that low-frequency motions have to be critically understood for all such D-A pairs, and generates a rational methodology for utilization of hydroxy-anthraquinone acceptors in numerous photoactive architectures.
authors.affiliation: Department of Chemical Sciences, Tata Institute of Fundamental Research , Mumbai 400005, India.
authors.forename: Ajay
authors.initials: A
authors.lastname: Jha
authors.forename: Debayan
authors.initials: D
authors.lastname: Chakraborty
authors.forename: Varadharajan
authors.initials: V
authors.lastname: Srinivasan
authors.forename: Jyotishman
authors.initials: J
authors.lastname: Dasgupta
mesh_terms: D000880:Anthraquinones / Q000737:chemistry*; D055664:Electrochemical Techniques; D007834:Lasers; D056004:Molecular Dynamics Simulation; D012997:Solvents / Q000737:chemistry; D013059:Spectrum Analysis, Raman
chemical_list: D000880:Anthraquinones; D012997:Solvents; C042834:9,10-anthraquinone