Role of Planar Conformations in Aggregation Induced Spectral Shifts of Supermolecular Oligofluorenols in Solutions and Films: A Combined Experimental and MD/TD-DFT Study

The supramolecular approach of fluorenol polymers brings about excellent self-assembly behavior to fabricate organogels and superstructured thin films through highly directional noncovalent interactions. To understand the aggregation effects on electronic structures, the packing structures and the UV/vis absorption spectra of oligofluorenols (PFOHn, n = 1/3–8), with and without OC8H17 side chains, were studied experimentally and theoretically in crystal, amorphous solids, and solutions, respectively. For the ground state in vacuum the steric repulsion between two adjacent fluorenol units renders the PFOH oligomers twisted in a helix conformation, while the molecular aggregation favors the appearance of planar π-conjugated structures. In comparison with the crystal packing, the content of planar conformation (with the torsion angle less than 20°) is increased in amorphous solids. The hydroxyl groups in oligofluorenols facilitate the formation of hydrogen bonding networks. The red shift in absorption spectr...