Quadrupolar D-π-A-π-D chromophores with central tetrafluorobenzene acceptor and two peripheral N,N-dimethylamino and methoxy donors

• Published in: Journal of fluorine chemistry Vol. 161; pp. 15 - 23
• Main Authors: Kulhánek, Jiří, Bureš, Filip, Pytela, Oldřich, Pippig, Falko, Danko, Martin, Mikysek, Tomáš, Padělková, Zdeňka, Ludwig, Miroslav
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.05.2014; Elsevier
• Subjects: Absorption/emission spectra; Acceptors (electronic); Chemical reactions; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Chromophores; Donors (electronic); Electrochemistry; Electronics; Mathematical analysis; Nonlinear optics; Physical Sciences; Push–pull chromophore; Science & Technology; Structure–property relationships; Tetrafluorobenzene; Tuning; Electrochemistry; Tetrafluorobenzene; Structure–property relationships; Absorption/emission spectra; Push–pull chromophore; Nonlinear optics; 2-PHOTON ABSORPTION; BEHAVIOR; OPTICAL-PROPERTIES; PUSH-PULL CHROMOPHORES; ORGANIC SEMICONDUCTORS; OLIGOMERS; LINKERS; Structure-property relationships; CHARGE-TRANSFER CHROMOPHORES; EFFICIENT; FLUORINE CHEMISTRY; Push-pull chromophore
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2014.02.002

Quadrupolar charge-transfer compounds with tetrafluorobenzene central acceptor and two peripheral donors separated by systematically enlarged π-linker were designed, synthesized and further studied by X-ray analysis, electrochemistry, absorption/emission spectra and calculations. Structure–property relationships were elucidated. •Ten new organic push–pull–push molecules with intramolecular charge transfer were synthesized.•Tuning of linear and nonlinear optical properties by the π-system extension and variation of the peripheral donors.•Thorough property study by X-ray analysis, electrochemistry, absorption/emission spectra and calculations.•Fundamental structure–property relationships. 1,2,4,5-Tetrafluorobenzene has been utilized as suitable central acceptor moiety in push–pull chromophores having D-π-A-π-D quadrupolar arrangement. Starting from commercially available 1,4-diiodotetrafluorobenzene, nine novel chromophores with systematically extended π-system were synthesized via cross-coupling reactions. Further electronic tuning has been achieved by variation of the appended donor (N,N-dimethylamino and methoxy groups). Target chromophores were further investigated by X-ray analysis, electrochemical measurements, absorption and emission spectra and theoretical calculations and structure–property relationships were elucidated. Whereas target chromophores showed weak second-order nonlinear responses with β of 0.18–6.09×10−30esu, which is primarily given by their centrosymmetric arrangement, third-order polarizabilities γ of 0.84–22.5×10−27esu notably exceeded the standard Disperse Red 1 (γ=3.47×10−27esu).