π-Extended fluoranthene imide derivatives: synthesis, structures, and electronic and optical properties

• Published in: Canadian journal of chemistry Vol. 95; no. 4; pp. 371 - 380
• Main Authors: Kawajiri, Ikumi, Nagahara, Masaya, Ishikawa, Hiroyuki, Yamamoto, Yuma, Nishida, Jun-ichi, Kitamura, Chitoshi, Kawase, Takeshi
• Format: Journal Article
• Language: English
• Published: OTTAWA NRC Research Press 01.04.2017; Canadian Science Publishing; Canadian Science Publishing NRC Research Press
• Subjects: Absorption; Absorption spectra; Agglomeration; Anhydrides; autoagrégation; Charge transfer; Chemical properties; Chemical reactions; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Coefficients; Crystal structure; Crystals; Density functional theory; Derivatives; Diels-Alder reactions; Dienes; Electrons; Emission; Excitation; fluoranthène à système π étendu; fluorophore; imides; Mathematical analysis; Molecular orbitals; Molecular structure; Molecules; NMR; Nuclear magnetic resonance; Observations; Optical properties; Physical Sciences; Planar structures; Polycyclic aromatic hydrocarbons; Science & Technology; self-aggregation; Separation; solvatochromism; solvatochromisme; structure cristalline; π-extended fluoranthene; fluorophore; FULLERENE SMALL-MOLECULE; CRYSTAL-STRUCTURE; pi-extended fluoranthene; INTRAMOLECULAR CHARGE-TRANSFER; DYES SYNTHESIS; imides; FLUORESCENCE; SOLVENTS; COLOR; crystal structure; EMISSION; solvatochromism; self-aggregation; AGGREGATION; ACCEPTOR
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/cjc-2016-0488

Diels–Alder reactions of acenaphthylene-5,6-dicarboximide ( AI ) derivatives with the corresponding dienes afforded some derivatives of π-extended fluoranthene imide, namely N-(2-ethylhexyl)-7,10-diphenylfluoranthene imide ( DPFI ) and N-(2-ethylhexyl)-7,8,9,10-tetraphenylfluoranthene imide ( TPFI ), N-(n-octyl)-benzo[k]fluoranthene imide ( BFI ), and N-(n-octyl)-naphtho[k]fluoranthene imide ( NFI ). Molecular structures of TPFI and BFI reveal that the core π-skeletons have a highly planar structure, and the molecules form a dimeric structure in the crystals. The absorption spectra exhibit bathochromic shift with π-extension of the core π-skeletons. On the other hand, DPFI and TPFI show the long-wavelength emission related to BFI , probably due to π-extension toward the phenyl substituents in the excited states. BFI and NFI exhibited an interesting concentration-dependent 1 H-NMR behavior in CDCl 3 , suggesting self-aggregation formation. Moreover, BFI and NFI show moderate and remarkable solvatofluorochromism in solutions ( BFI for Δλ EM = 67 nm, NFI for Δλ EM = 116 nm), respectively, while DPFI and TPFI show weak solvatofluorochromism. The density functional theory calculations demonstrate that the considerable spatial separation between the HOMO and LUMO coefficients in the NFI molecule. The result indicates that the ground-to-excited state transition of NFI should have intramolecular charge transfer (ICT) character.