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BODIPY‐Bridged Push–Pull Chromophores for Nonlinear Optical Applications
Author(s) -
Ulrich Gilles,
Barsella Alberto,
Boeglin Alex,
Niu Songlin,
Ziessel Raymond
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201402123
Subject(s) - bodipy , moiety , chromophore , chemistry , protonation , photochemistry , solvatochromism , tetracyanoethylene , electron acceptor , hyperpolarizability , electron donor , acceptor , fluorescence , stereochemistry , organic chemistry , molecule , ion , physics , quantum mechanics , polarizability , catalysis , condensed matter physics
A set of linear and dissymmetric BODIPY‐bridged push–pull dyes are synthesized. The electron‐donating substituents are anisole and dialkylanilino groups. The strongly electron‐accepting moiety, a 1,1,4,4‐tetracyanobuta‐1,3‐diene (TCBD) group, is obtained by insertion of an electron‐rich ethyne into tetracyanoethylene. A nonlinear push–pull system is developed with a donor at the 5‐position of the BODIPY core and the acceptor at the 2‐position. All dyes are fully characterized and their electrochemical, linear and nonlinear optical properties are discussed. The linear optical properties of dialkylamino compounds show strong solvatochromic behavior and undergo drastic changes upon protonation. The strong push–pull systems are non‐fluorescent and the TCBD‐BODIPY dyes show diverse photochemistry and electrochemistry, with several reversible reduction waves for the tetracyanobutadiene moiety. The hyperpolarizability μβ of selected compounds is evaluated using the electric‐field‐induced second‐harmonic generation technique. Two of the TCBD‐BODIPY dyes show particularly high μβ (1.907 μm) values of 2050×10 −48 and 5900×10 −48 esu. In addition, one of these dyes shows a high NLO contrast upon protonation–deprotonation of the donor residue.