Tuning Redox Properties and Self‐Assembly of Thienoacene‐Extended Tetrathiafulvalenes

Cecilie Lindholm Andersen; Michal Zalibera; Karol Lušpai; Mikkel A. Christensen; Denisa Darvasiová; Vladimír Lukeš; Peter Rapta; Michael M. Haley; Ole Hammerich; Mogens Brøndsted Nielsen

doi:10.1002/cplu.201800626

Tuning Redox Properties and Self‐Assembly of Thienoacene‐Extended Tetrathiafulvalenes

Cecilie Lindholm Andersen, Michal Zalibera, Karol Lušpai, Mikkel A. Christensen, Denisa Darvasiová, Vladimír Lukeš, Peter Rapta, Michael M. Haley, Ole Hammerich, Mogens Brøndsted Nielsen

Department of Chemistry

2 Citations (Scopus)

Abstract

Turning on and off associations between molecules by a reversible change in their redox states is a convenient way of controlling self-assembly and hence for advancing supramolecular chemistry. Here we present systematic studies on a selection of extended tetrathiafulvalenes with thienoacene spacers. By cyclic and differential pulse voltammetry and in situ EPR/UV-Vis-NIR spectroelectrochemistry, in combination with computations, we have elucidated how the number and orientations of thiophene rings in the spacer between the two dithiafulvene rings influence both the donor strength and association properties. The radical cations and their associates were found to cover a remarkable large region of the UV-Vis-NIR spectrum, but the appearance of the absorption spectrum of the radical cations as well as of the unassociated dications also depended strongly on the exact molecular structure.

Original language	English
Journal	ChemPlusChem
Volume	84
Issue number	9
Pages (from-to)	1279-1287
ISSN	2192-6506
DOIs	https://doi.org/10.1002/cplu.201800626
Publication status	Published - 1 Sept 2019

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abstract = "Turning on and off associations between molecules by a reversible change in their redox states is a convenient way of controlling self-assembly and hence for advancing supramolecular chemistry. Here we present systematic studies on a selection of extended tetrathiafulvalenes with thienoacene spacers. By cyclic and differential pulse voltammetry and in situ EPR/UV-Vis-NIR spectroelectrochemistry, in combination with computations, we have elucidated how the number and orientations of thiophene rings in the spacer between the two dithiafulvene rings influence both the donor strength and association properties. The radical cations and their associates were found to cover a remarkable large region of the UV-Vis-NIR spectrum, but the appearance of the absorption spectrum of the radical cations as well as of the unassociated dications also depended strongly on the exact molecular structure.",

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doi = "10.1002/cplu.201800626",

language = "English",

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T1 - Tuning Redox Properties and Self‐Assembly of Thienoacene‐Extended Tetrathiafulvalenes

AU - Lindholm Andersen, Cecilie

AU - Zalibera, Michal

AU - Lušpai, Karol

AU - Christensen, Mikkel A.

AU - Darvasiová, Denisa

AU - Lukeš, Vladimír

AU - Rapta, Peter

AU - Haley, Michael M.

AU - Hammerich, Ole

AU - Brøndsted Nielsen, Mogens

PY - 2019/9/1

Y1 - 2019/9/1

N2 - Turning on and off associations between molecules by a reversible change in their redox states is a convenient way of controlling self-assembly and hence for advancing supramolecular chemistry. Here we present systematic studies on a selection of extended tetrathiafulvalenes with thienoacene spacers. By cyclic and differential pulse voltammetry and in situ EPR/UV-Vis-NIR spectroelectrochemistry, in combination with computations, we have elucidated how the number and orientations of thiophene rings in the spacer between the two dithiafulvene rings influence both the donor strength and association properties. The radical cations and their associates were found to cover a remarkable large region of the UV-Vis-NIR spectrum, but the appearance of the absorption spectrum of the radical cations as well as of the unassociated dications also depended strongly on the exact molecular structure.

AB - Turning on and off associations between molecules by a reversible change in their redox states is a convenient way of controlling self-assembly and hence for advancing supramolecular chemistry. Here we present systematic studies on a selection of extended tetrathiafulvalenes with thienoacene spacers. By cyclic and differential pulse voltammetry and in situ EPR/UV-Vis-NIR spectroelectrochemistry, in combination with computations, we have elucidated how the number and orientations of thiophene rings in the spacer between the two dithiafulvene rings influence both the donor strength and association properties. The radical cations and their associates were found to cover a remarkable large region of the UV-Vis-NIR spectrum, but the appearance of the absorption spectrum of the radical cations as well as of the unassociated dications also depended strongly on the exact molecular structure.

U2 - 10.1002/cplu.201800626

DO - 10.1002/cplu.201800626

M3 - Journal article

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VL - 84

SP - 1279

EP - 1287

JO - ChemPlusChem

JF - ChemPlusChem

IS - 9

ER -

Tuning Redox Properties and Self‐Assembly of Thienoacene‐Extended Tetrathiafulvalenes

Abstract

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