Ultrafast Structure and Vibrational Dynamics of a Cyano-Containing Non-Fullerene Acceptor for Organic Solar Cells Revealed by Two-Dimensional Infrared Spectroscopy.

Non-fullerene molecules, such as ITIC (3,9-bis(2-methylene-(3-(1,1-dicyanomethylene) indanone)-5,5,11,11-tetrakis(4-hexylphenyl)dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene), are among the most promising non-fullerene acceptors for organic solar cells (OSCs). In this work, using the cyano stretching mode as a vibrational marker, the structural and vibrational energy dynamics of ITIC were examined on an ultrafast time scale with two-dimensional infrared spectroscopy. Two IR-active modes studied here mainly correspond to two anti-symmetric combinations of symmetric and asymmetric stretching vibrations of two C≡N modes originating from two -C(CN)2 chromophores that are located across the ITIC system, which were found to have significantly larger off-diagonal anharmonicity than their corresponding diagonal anharmonicities. This indicates strong anharmonic vibrational coupling between the two modes, which is supported by ab initio anharmonic frequency computations. Transient IR results indicate picosecond intramolecular vibrational energy transfer between the two C≡N modes upon excitation. The structural basis for these vibrational and energetic features is the conjugating molecular frame that is composed of a network of single/double bonds connecting the two -C(CN)2 chromophores and may enable efficient vibration delocalization, in addition to its well-known electron delocalization capability. The importance of the results for the OSC applications is discussed.