A structure–effect study is presented pertaining to the HOMO–LUMO tuning of compounds built upon the 9-fluorenylidene scaffold frequently incorporated as a moiety within organic-based semiconducting materials. The results represent the first reported analysis employing an ensemble of spectroscopy, electrochemistry, and crystal structure data to elucidate and compare the electronic properties of 9-fluorenones, 9-fluorenylidenes, and 9-fluorenimine derivatives. The results also provide the first spectroscopically and crystallographically measured description of exciton coupling within 9,9′-bifluorenylidenes. The 9-ylidene bond is seen to play a key role impacting the electronic properties, and an examination of the effects of substituents, conjugation, heteroatoms, and steric strain on the 9-ylidene bond in a diverse set of structures with representative structural variations relevant to the HOMO–LUMO tuning is presented. Increasing conjugation decreased the HOMO–LUMO gap (HLG), increased the HOMO energy (EHOMO), but decreased the LUMO energy (ELUMO). Substituent effects were observed to produce only slight changes that tended to decrease the HLG and increase both EHOMO and ELUMO, while heteroatom inclusion at the 9-ylidine bond tended to decrease the HLG, EHOMO, ELUMO, and the extinction coefficient. In the sterically hindered 9,9′-bifluorenylidenes, increased steric strain that promoted either an increase in the torsion angle or bond length of the 9-ylidene bond was seen to decrease the HLG via exciton coupling. These results elucidate the HOMO–LUMO tuning of systems containing a 9-fluorenylidene moiety and may assist in developing materials with specifically tuned HLGs and HOMO–LUMO levels for a variety of applications.
Theoretical analysis of [5.5.6]cyclacenes: electronic properties, strain energies and substituent effects
