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

Abstract

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 1H-NMR behavior in CDCl3, suggesting self-aggregation formation. Moreover, BFI and NFI show moderate and remarkable solvatofluorochromism in solutions (BFI for ΔλEM = 67 nm, NFI for ΔλEM = 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.

Isolation and characterisation of a stable 2-azaphenalenyl azomethine ylide

“…This observation demonstrates that the corresponding azomethine ylide 7a is generated as a reactive intermediate by Et 3 N induced deprotonation of 8a. Additionally, reaction of 7a with the as a versatile synthetic intermediate [16][17][18][19] N-(2-ethylhexyl) acenphthylene-5,6-dicarboxylimide 11 was examined. Under similar conditions, this reaction produces the corresponding cycloadduct 12 in 31% yield ( Fig.…”

Highly Polarized Benzo[k]fluoranthene Imide Derivatives: Large Solvatofluorochromism, Dual Fluorescence and Aggregation Induced Emission Associated with Excited‐State Intramolecular Charge Transfer

“… a) Absorption and b) normalized fluorescence spectra ( λ EX =350 nm for 2 a , λ EX =365 nm for 5 a , 6 a , and 7 b , ca. 10 −5 M) of the BFI derivatives, 2 a , 5 a , 6 a and 7 b in DCM.…”

“…Synthesis : N ‐(2‐Ethylhexyl)‐acenaphthylene‐5,6‐dicarboxyimide ( 4 a ) and N ‐(octyl)‐acenaphthylene‐5,6‐dicarboxyimide ( 4 b ) were prepared from acenaphthene using a reported procedure . 1,2‐dibromo‐4,5‐bis(dibromomethyl)benzene ( 8 ) was prepared from 4,5‐dibromoxylene…”

“…Recently, we described a method for the synthesis of π‐extended fluoranthene imides derivatives that is based on the use of acenaphthylene‐5,6‐dicarboximides (AI, 1 ), which contain a highly reactive C−C double bond . We observed that, among members of this group, benzo[ k ]fluoranthene 3,4‐dicarboximide (BFI) 2 a and naphtho[ k ]fluoranthene 3,4‐dicarboximide 3 a in organic solvents display moderate and large solvatofluorochromism SFC . In an extension of this study, we designed a new group of BFI based push‐pull substances that possess an arylamine group at one end of an arene moiety.…”

Synthesis and Properties of a Decacyclene Monoimide and a Naphthalimide Derivative as Three‐Dimensional Acceptor–Donor–Acceptor Systems

“…As a result, imides containing PAHs have “push–pull” character . Recently, as part of studies exploring substances that have push–pull structures, we recently synthesized fluoranthene–naphthalimide 7 by DA reaction of 6 b with an appropriate o ‐xylylene derivative . We observed that naphthalimide 7 displayed interesting properties such as solvatofluorochromism in organic solvents and self‐aggregation in CDCl 3 .…”