Twisted intramolecular charge transfer (TICT) chromophores exhibit uniquely large second-order optical nonlinearities (μβ). However, their promise as electro-optic (E-O) materials is yet untapped, reflecting a strong tendency to aggregate in low-polarity media, leading to a dramatic fall in μβ. Until now, TICT chromophores in deaggregating polar solvents suffered decreased response due to polarity-driven changes in electronic structure. Here we report a new series of benzimidazolium-based TICT chromophores with interaryl torsional angles in the range of 64-77°. The most twisted, B2TMC-2, exhibits a large μβvec= -26,000 × 10-48esu (at 1907 nm) in dilute nonpolar CH2Cl2solution, which is maintained in polar DMF (μβvec= -20,370 × 10-48esu) as measured by DC electric field-induced second harmonic generation (EFISH). Sterically enforced interaryl torsional angles are confirmed by single-crystal X-ray diffraction and solution phase Nuclear Overhauser Effect (NOE) NMR, and spectroscopic characterization reveals a zwitterionic/aromatic ground state electronic structure associated with the high μβ. We show that increasingly disrupted conjugation is correlated with increased μβ even at intermediate twist angles. The excellent performance and reduced aggregation in polar solvents opens new avenues for bridging microscopic and macroscopic chromophore performance.
Unprecedented Large Hyperpolarizability of Twisted Chromophores in Polar Media / A.J.-. Lou, S. Righetto, C. Barger, C. Zuccaccia, E. Cariati, A. Macchioni, T.J. Marks. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 140:28(2018 Jul 18), pp. 8746-8755.
|Titolo:||Unprecedented Large Hyperpolarizability of Twisted Chromophores in Polar Media|
CARIATI, ELENA (Corresponding)
|Parole Chiave:||Catalysis; Chemistry (all); Biochemistry; Colloid and Surface Chemistry|
|Settore Scientifico Disciplinare:||Settore CHIM/03 - Chimica Generale e Inorganica|
|Data di pubblicazione:||18-lug-2018|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1021/jacs.8b04320|
|Appare nelle tipologie:||01 - Articolo su periodico|