Abstract
Densityโfunctional theory studies were applied to investigate the structural, electronic, and optical properties of 9โheterofluorenes achieved by substituting the carbon at 9 position of fluorene with silicon, germanium, nitrogen, phosphor, oxygen, sulfur, selenium, or boron. These heterofluorenes and their oligomers up to pentamers are highly aromatic and electrooptically active. The alkyl and aryl substituents of the heteroatom have limited influence, but the oxidation of the atom has significant influence on their molecular structures and properties. The highest occupied molecular orbital (HOMO)โlowest occupied molecular orbital (LUMO) interaction theory was successfully applied to analyze the energy levels and the frontier wave functions of these heterofluorenes. Most heterofluorenes belong to type B of interaction with lowโlying LUMO and have the second kind of wave function. Carbazole and selenafluorene have type C of interaction with highโlying HOMO and the third kind of wave function. Types C and D of heterofluorenes, such as carbazole, oxygafluorene, sulfurafluorene, and selenafluorene also have high triplet state energies. The extrapolated HOMO and LUMO for polyheterofluorenes indicate that polyselenonafluorene has the lowest LUMO; polycarbazole has the highest HOMO; polyselenafluorene has the highest bandgap (E~g~); and polyborafluorene has the lowest E~g~. Heterofluorenes and their oligomers and polymers are of great experimental interests, especially those having extraordinary properties revealed in this study. ยฉ 2007 Wiley Periodicals, Inc. J Comput Chem, 2007