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Supersonically cooled, π-conjugated molecular cluster anions are efficiently produced up to more than 100 constituent molecules and their electronic states are size-selectively investigated using anion photoelectron spectroscopy. Homogeneous anionic clusters of anthracene, (anthracene)n- (n = 1-100), are presented herein as one of noteworthy results among those studies. The coexistence of two types of anionic isomers is found over a broad range in size: isomers I and II-1 (n = 4-30) or isomers I and II-2 (n ≥ 40). Size-dependent energetics, vibrational features, and temperature variations of photoelectron spectra for each isomer allow us to infer their structural motifs, electron accommodation modes, and formation mechanisms. Such improved knowledge increases our comprehension about size effect on cooperative nature between electronic states and structures of π-conjugated molecular aggregates at a molecular-level.

Size Effect on Cooperative Nature between Electronic States and Structures of π-Conjugated Molecular Aggregates