Fundamental Study of the Optical and Vibrational Properties of Fx-AZB@MOF Systems As Functions of Dye Substitution and the Loading Amount

Overview

Journal Langmuir

Publisher American Chemical Society

Specialty Chemistry

Date 2022 Mar 28

PMID 35344366

Authors

Markus Rodl

Alen Reka

Marko Panic

Alexander Fischereder

Marco Oberlechner

Thomas Mairegger

Holger Kopacka

Hubert Huppertz

Thomas S Hofer

Heidi A Schwartz

Affiliations

Soon will be listed here.

Abstract

Controlling the switching efficiency of photoactive hybrid systems is an obligatory key prerequisite for systematically improving the design of functional materials. By modulating the degree of fluorination and the amount being embedded into porous hosts, the / ratios of fluorinated azobenzenes were adjusted as both functions of substitution and the degree of loading. Octafluoroazobenzene (F8-AZB) and perfluoroazobenzene (F10-AZB) were inserted into porous DMOF-1. Especially for perfluoroazobenzene (F10-AZB), an immense stabilization of the isomer was observed. In complementary molecular dynamics simulations performed at the DFTB (density functional tight binding) level, an in-depth characterization of the interactions of the different photoisomers and the host structure was carried out. On the basis of the resulting structural and energetic data, the experimentally observed increase in the amount of the conformer for F8-AZB can be explained, while the stabilization of -F10-AZB can be directly related to a fundamentally different interaction motif compared to its tetra- and octafluorinated counterparts.

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