A distinctive example of the cooperative interplay of structure and environment in tuning of intramolecular charge transfer in second-order nonlinear optical chromophores

Alessandro Abbotto*, Luca Beverina, Silvia Bradamante, Antonio Facchetti, Christopher Klein, Giorgio A. Pagani, Mesfin Redi-Abshiro, Rüdiger Wortmann

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

172 Scopus citations

Abstract

The strongly enhanced cooperative influence of medium polarity and organic structural design on the first hyperpolarizability β of a novel family of highly polarizable azinium-(CH=CH-thienyl)-dicyanomethanido chromophores 1-3 is described. The dyes can be efficiently synthesized by regioselectire protonation/alkylation of the corresponding bidentate anion precursors. Consecutive annelation of the pyridyl ring of 1 (pyridine → quinoline → acridine) and medium polarity effects are responsible for an extraordinarily variable range of intramolecular charge transfer (ICT), leading to a large set of π-electron distribution patterns. Accordingly, systems with remarkably different zwitterionic/quinoid character in the ground and excited states present β values in a broad range, eventually switching from negative to positive. Our investigation is based on a combination of experimental (UV/Vis spectroscopy, multinuclear NMR spectroscopy, and electrooptical absorption measurements) and computational (ab initio) approaches. It is shown that: 1) β and μβ are dramatically influenced, even by orders of magnitude, by a complex, non-monotonic interplay of structure and medium action, which in turn affects molecular ICT and bond length alternation (BLA), 2) the computations, validated by different experimental data, are to be recommended as an extremely useful tool in the search for a greatly improved set of molecular nonlinear optical (NLO) responses (in the case of 1-3 they show that such conditions may be attained only in a narrow and limited range of dielectric constants in which the annelation effect operates most efficiently), and 3) the search for the most favorable molecular NLO response of a highly polarizable chromophore both in solution and in solid matrices should simultaneously take into account not only the molecular design supplemented by annelation effects but also the polarity of the medium.

Original languageEnglish (US)
Pages (from-to)1991-2007
Number of pages17
JournalChemistry - A European Journal
Volume9
Issue number9
DOIs
StatePublished - May 9 2003

Keywords

  • Ab initio calculations
  • Annelation
  • Heterocyclic zwitterions
  • NMR spectroscopy
  • Nonlinear optics

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis
  • Organic Chemistry

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