Issue 3, 2016

Effect of intercalation and chromophore arrangement on the linear and nonlinear optical properties of model aminopyridine push–pull molecules

Abstract

Three push–pull aminopyridine derivatives having D–π–A, D–(π–A)2, and D–(π–A)3 arrangements were examined as model organic chromophores capable of intercalation into inorganic layered materials (alpha modification of zirconium hydrogen phosphate, zirconium 4-sulfophenylphosphonate, and gamma modification of titanium hydrogen phosphate). The fundamental properties of these dyes, their methylated analogues as well as their intercalates were studied by X-ray analysis, electrochemistry, UV/Vis absorption spectra, TGA, IR spectra, SHG, and were completed by DFT calculations. The synthesis of tripodal tris(pyridin-4-yl)amine is given for the first time. The HOMO–LUMO gap, the position of the longest-wavelength absorption maxima, and the dipole moment of aminopyridines can easily be tuned by attaching/removing pyridin-4-yl electron withdrawing units and their quaternization (pyridine vs. pyridinium acceptors). Their intercalation proved to be feasible affording novel inorganic–organic hybrid materials. The intercalation is accompanied by protonation of the guest, which enhances its ICT and strongly anchors the aminopyridines into the confined space of the layered host. Moreover, this process results in ordering of the organic chromophores and also brings improved thermal and chemical robustness. As a result, the measured SHG efficiencies of the intercalates are larger than those observed for the pure organic push–pull chromophores. Hence, the methodology of intercalation turned out to be very useful strategy for property tuning of NLO-active organic molecules.

Graphical abstract: Effect of intercalation and chromophore arrangement on the linear and nonlinear optical properties of model aminopyridine push–pull molecules

Supplementary files

Article information

Article type
Paper
Submitted
26 Oct 2015
Accepted
01 Dec 2015
First published
02 Dec 2015
This article is Open Access
Creative Commons BY-NC license

J. Mater. Chem. C, 2016,4, 468-478

Author version available

Effect of intercalation and chromophore arrangement on the linear and nonlinear optical properties of model aminopyridine push–pull molecules

F. Bureš, D. Cvejn, K. Melánová, L. Beneš, J. Svoboda, V. Zima, O. Pytela, T. Mikysek, Z. Růžičková, I. V. Kityk, A. Wojciechowski and N. AlZayed, J. Mater. Chem. C, 2016, 4, 468 DOI: 10.1039/C5TC03499J

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements