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Rational Design of Push–Pull Fluorene Dyes: Synthesis and Structure–Photophysics Relationship
Author(s) -
Shaya Janah,
FontaineVive Fabien,
Michel Benoît Y.,
Burger Alain
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201600581
Subject(s) - fluorene , photochemistry , chemistry , acceptor , combinatorial chemistry , organic chemistry , polymer , physics , condensed matter physics
Our work surveyed experimental and theoretical investigations to construct highly emissive D –π–A (D=donor, A=acceptor) fluorenes. The synthetic routes were optimised to be concise and gram‐scalable. The molecular design was first rationalised by varying the electron‐withdrawing group from an aldehyde, ketotriazole or succinyl to methylenemalonitrile or benzothiadiazole. The electron‐donating group was next varied from aliphatic or aromatic amines to saturated cyclic amines ranging from aziridine to azepane. Spectroscopic studies correlated with TD‐DFT calculations provided the optimised structures. The selected push–pull dyes exhibited visible absorptions, significant brightness, important solvatofluorochromism, mega‐Stokes shifts (>250 nm) and dramatic shifts in emission to the near‐infrared. The current library includes the comprehensive characterization of 16 prospective dyes for fluorescence applications. Among them, several fluorene derivatives bearing different conjugation anchors were tested for coupling and demonstrated to preserve the photophysical responses once further bound.