Interplay of twist angle and solvents with two-photon optical channel interference in aryl-substituted BODIPY dyes

Abstract

a Channel interference plays a crucial role in understanding the physics behind multiphoton absorption processes. In this work, we study the role of channel interference and solvent effects on the two-photon absorption in aryl-substituted boron dipyrromethene (BODIPY) dyes, a class of intramolecular charge-transfer (ICT) molecules. For this purpose, we consider fourteen dyes of this class with various donor/acceptor substitutions at the para position of the phenyl ring and with or without methyl (-CH 3 ) substitution on the BODIPY moiety. The presence of a methyl group on the BODIPY moiety affects the dihedral angle significantly, which in turn affects the one-(OPA) and two-photon absorption (TPA) properties of the molecules.Among the molecules studied, the one having the strong electron-donating dimethylamino group and no methyl substitution at the BODIPY moiety is found to have the highest TPA cross section. Our few-state model analysis shows that the large TPA activity of this molecule is due to the all positive contributions from different channel interference terms. Change in dielectric constant of the medium is found to have a profound impact on both the magnitude and sign of the channel interference terms. The magnitude of destructive channel interference gradually decreases with decreasing solvent polarity and becomes constructive in a low-polarity solvent. We also study the effect of rotating the phenyl ring with respect to the BODIPY moiety on the TPA activity. In the gas phase and in different solvents, we found that channel interference is changed from destructive to constructive on twisting the molecule. These results are explained by considering different dipole-, energy-and angle-terms appearing in the expression of a two-state model.

Enhanced Two–Photon Absorption and Promising Broad Energy Range Optical Power Limiting Properties ofTransoidandCisoidBenzodipyrrolenine-Fused Squaraine Dimers

“…Assuming that the permanent dipole moments of the ground and final states are parallel as expected for the C 2v point group, eq 2 results with θ gf being the angle between Δμ gf and μ gf . 66 Both two-photon transition models are sketched in Figure 2.…”

Dynamics of the excited-state hydrogen transfer in a (dG)·(dC) homopolymer: intrinsic photostability of DNA

“…The first one is the time-dependent density functional theory (TD-DFT) method using the long-range corrected hybrid CAM-B3LYP functional as implemented in the GAUSSIAN 09 software package. 28 The choice of the CAMB3LYP functional to compute the excited states is based on its proven good description of charge-transfer (CT) states 29 of organic molecules, 30 – 32 in particular, photoinduced processes in DNA and related systems. 33 – 41 The second QM method is the ab initio complete-active-space second-order perturbation theory (CASPT2) as implemented in the MOLCAS 8 software package.…”

Spectral shifts of BODIPY derivatives: a simple continuous model

“…30 It has previously been used to investigate BODIPY dyes and other fluorophores. 21,[35][36][37] 3 Results and discussion…”