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New [2,2]Fluorenophanes with Unexplored Insight: Asymmetric Charge Transfer-Mediated Exciton Delocalization along the π-π Packing Direction.

A series of new [2,2] fluorenophanes  were synthesized and characterized, among which molecules of crystallographically asymmetric  anti-[2.2](1,4)(4,1)fluorenophane ( K2C-2) aggregate to form one-dimensional  supramolecular  chain structures through effective intermolecular  π-π  overlapping . This, in combination with the synergistic intramolecular  π-π  interaction, leads to prominent dual emission  mediated by charge transfer (CT) exciton delocalization. Support of this new insight is given by mapping the transition density along  the π-π  packing direction where the intramolecular  excitation and intermolecular CT coexist in  K2C-2.