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Issue 28, 2015

Synthesis, chiroptical and SHG properties of polarizable push–pull dyes built on π-extended binaphthyls

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Abstract

We report on new enantiopure binaphthyl derivatives in which electron-donating and electron-withdrawing substituents are placed in direct conjugation, to create active push–pull dyes for NLO applications. The dyes, unprecedentedly, extend their π-bridge from the 3,3′ positions of the binaphthyl units, and incorporate as acceptors pyridine units, possessing a coordinating nitrogen atom useful for further supramolecular polarization of the chiral dyes. The π-bridge is constructed by the sequential attachment of phenylenevinylene units to the enantiopure binaphthyl derivatives through Horner–Wadsworth–Emmons olefination, which proceed with high stereoselectivity, affording stereodefined chiral dyes. The polarization of the terminal pyridine units by means of labile complexation with Pd2+ ions has been demonstrated using both optical and chiroptical methods. The polarization by protonation can be made reversible in solution and solid state by exposure to ammonia vapors, as shown by absorption and emission spectroscopies. NLO properties, as determined by EFISH generation measurements in solution, are significant for the bisprotonated species when compared to previously reported binaphthyl substrates. TDDFT calculations show that the hyperpolarizability tensor contribution is responsible for enhancing SHG values upon protonation up to one order of magnitude, highlighting the potential of such ortho related, axially-chiral push–pull dyes for functional NLO applications.

Graphical abstract: Synthesis, chiroptical and SHG properties of polarizable push–pull dyes built on π-extended binaphthyls

Supplementary files

Article information


Submitted
22 Dec 2014
Accepted
19 Feb 2015
First published
19 Feb 2015

This article is Open Access

RSC Adv., 2015,5, 21495-21503
Article type
Paper
Author version available

Synthesis, chiroptical and SHG properties of polarizable push–pull dyes built on π-extended binaphthyls

C. Coluccini, M. Caricato, E. Cariati, S. Righetto, A. Forni and D. Pasini, RSC Adv., 2015, 5, 21495 DOI: 10.1039/C4RA16876C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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