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Large Quadratic Hyperpolarizabilities with Donor–Acceptor Polyenes Exhibiting Optimum Bond Length Alternation: Correlation Between Structure and Hyperpolarizability
Author(s) -
BlanchardDesce M.,
Alain V.,
Bedworth P. V.,
Marder S. R.,
Fort A.,
Runser C.,
Barzoukas M.,
Lebus S.,
Wortmann R.
Publication year - 1997
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.19970030717
Subject(s) - hyperpolarizability , chromophore , chemistry , bathochromic shift , conjugated system , polarizability , dipole , computational chemistry , acceptor , ground state , photochemistry , crystallography , polymer , molecule , organic chemistry , atomic physics , optics , quantum mechanics , physics , fluorescence
Donor–acceptor polyenes of various lengths, and that combine aromatic electron‐donating moieties with powerful heterocyclic electron‐withdrawing terminal groups, have been synthesized and characterized as efficient nonlinear optical (NLO) chromophores. Their linear and nonlinear optical properties have been investigated, and variations in these properties have been related to ground‐state polarization (dipole μ) and structure. In particular, unprecedented quadratic hyperpolarizabilities (β) have been achieved (up to β(0) = 1500 × 10 −30 esu) by reduction of the bond‐length alternation (BLA) in the polyenic chain. In each series of homologous compounds, increasing the number n of conjugated double bonds in the polyenic chain results in a marked bathochromic shift, more pronounced BLA, and exponential increases in μβ(0) values. As a result, polyenic chromophores displaying excellent optical quadratic nonlinearities (μβ values as large as 100 times that of the quadratic NLO benchmark 4‐dimethyl‐amino‐4′‐nitrostilbene (DANS)), as well as satisfactory solubility, have been obtained.