Tetrathiafulvalene-oligofluorene star-shaped systems: new semiconductor materials for fluorescent moisture indicators

Katrina Scanlan, Alexander L. Kanibolotsky, Benjamin Breig, Gordon J. Hedley, Peter J. Skabara (Editor)

Research output: Contribution to journalArticle

Abstract

A series of novel star-shaped oligofluorene–thiophene–tetrathiafulvalene systems have been synthesised, following different synthetic routes. Each system incorporates a tetrathiafulvalene redox-active centre and four oligofluorene arms, providing a two-dimensional character to the conjugated backbone. The oligomers differ in the number of fluorene units present in the arms (1 to 4) and the terminal groups at the end of each arm (H or trimethylsilyl). Half-unit oligofluorene systems possessing a 1,3-dithiole-2-one core (a known precursor to the tetrathiafulvalene centre) have been synthesised in order to compare the thermal, optical and electrochemical properties. These half-unit systems consist of a 1,3-dithiole-2-one core fused to a thiophene unit at the 3- and 4-positions. Two oligofluorene arms consisting of 1 to 4 monomer units per arm are positioned at the 4- and 6-positions of the thiophene unit, affording extended conjugation through the thiophene centre. The half-unit systems are found to be moderate emitters in solution, however, the star-shaped systems bearing the tetrathiafulvalene core exhibit inhibited fluorescence in both solution and the solid state. We have demonstrated that the emission of the tetrathiafulvalene systems can be enhanced through the oxidation of the redox-centre followed by a consecutive reaction of the strongly electrophilic tetrathiafulvalene dication with such nucleophiles as water and hydrazine. The result of these reactions leads to an increase in the photoluminescence of these systems, affording the opportunity for the tetrathiafulvalene materials to be used as photonic materials in moisture indicators.
LanguageEnglish
Pages6582-6591
Number of pages10
JournalJournal of Materials Chemistry. C
Volume7
Issue number22
Early online date18 Mar 2019
DOIs
Publication statusPublished - 14 Jun 2019

Fingerprint

Thiophene
Stars
Moisture
Thiophenes
Semiconductor materials
Bearings (structural)
hydrazine
Nucleophiles
Hydrazine
Electrochemical properties
Oligomers
Photonics
Photoluminescence
Thermodynamic properties
Optical properties
Monomers
Fluorescence
Oxidation
tetrathiafulvalene
Water

Keywords

  • tetrathiafulvalene
  • molecular building blocks
  • electroactive organic material

Cite this

Scanlan, Katrina ; Kanibolotsky, Alexander L. ; Breig, Benjamin ; Hedley, Gordon J. ; Skabara, Peter J. (Editor). / Tetrathiafulvalene-oligofluorene star-shaped systems : new semiconductor materials for fluorescent moisture indicators. In: Journal of Materials Chemistry. C . 2019 ; Vol. 7, No. 22. pp. 6582-6591.
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Tetrathiafulvalene-oligofluorene star-shaped systems : new semiconductor materials for fluorescent moisture indicators. / Scanlan, Katrina; Kanibolotsky, Alexander L.; Breig, Benjamin; Hedley, Gordon J.; Skabara, Peter J. (Editor).

In: Journal of Materials Chemistry. C , Vol. 7, No. 22, 14.06.2019, p. 6582-6591.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Tetrathiafulvalene-oligofluorene star-shaped systems

T2 - Journal of Materials Chemistry. C

AU - Scanlan, Katrina

AU - Kanibolotsky, Alexander L.

AU - Breig, Benjamin

AU - Hedley, Gordon J.

A2 - Skabara, Peter J.

PY - 2019/6/14

Y1 - 2019/6/14

N2 - A series of novel star-shaped oligofluorene–thiophene–tetrathiafulvalene systems have been synthesised, following different synthetic routes. Each system incorporates a tetrathiafulvalene redox-active centre and four oligofluorene arms, providing a two-dimensional character to the conjugated backbone. The oligomers differ in the number of fluorene units present in the arms (1 to 4) and the terminal groups at the end of each arm (H or trimethylsilyl). Half-unit oligofluorene systems possessing a 1,3-dithiole-2-one core (a known precursor to the tetrathiafulvalene centre) have been synthesised in order to compare the thermal, optical and electrochemical properties. These half-unit systems consist of a 1,3-dithiole-2-one core fused to a thiophene unit at the 3- and 4-positions. Two oligofluorene arms consisting of 1 to 4 monomer units per arm are positioned at the 4- and 6-positions of the thiophene unit, affording extended conjugation through the thiophene centre. The half-unit systems are found to be moderate emitters in solution, however, the star-shaped systems bearing the tetrathiafulvalene core exhibit inhibited fluorescence in both solution and the solid state. We have demonstrated that the emission of the tetrathiafulvalene systems can be enhanced through the oxidation of the redox-centre followed by a consecutive reaction of the strongly electrophilic tetrathiafulvalene dication with such nucleophiles as water and hydrazine. The result of these reactions leads to an increase in the photoluminescence of these systems, affording the opportunity for the tetrathiafulvalene materials to be used as photonic materials in moisture indicators.

AB - A series of novel star-shaped oligofluorene–thiophene–tetrathiafulvalene systems have been synthesised, following different synthetic routes. Each system incorporates a tetrathiafulvalene redox-active centre and four oligofluorene arms, providing a two-dimensional character to the conjugated backbone. The oligomers differ in the number of fluorene units present in the arms (1 to 4) and the terminal groups at the end of each arm (H or trimethylsilyl). Half-unit oligofluorene systems possessing a 1,3-dithiole-2-one core (a known precursor to the tetrathiafulvalene centre) have been synthesised in order to compare the thermal, optical and electrochemical properties. These half-unit systems consist of a 1,3-dithiole-2-one core fused to a thiophene unit at the 3- and 4-positions. Two oligofluorene arms consisting of 1 to 4 monomer units per arm are positioned at the 4- and 6-positions of the thiophene unit, affording extended conjugation through the thiophene centre. The half-unit systems are found to be moderate emitters in solution, however, the star-shaped systems bearing the tetrathiafulvalene core exhibit inhibited fluorescence in both solution and the solid state. We have demonstrated that the emission of the tetrathiafulvalene systems can be enhanced through the oxidation of the redox-centre followed by a consecutive reaction of the strongly electrophilic tetrathiafulvalene dication with such nucleophiles as water and hydrazine. The result of these reactions leads to an increase in the photoluminescence of these systems, affording the opportunity for the tetrathiafulvalene materials to be used as photonic materials in moisture indicators.

KW - tetrathiafulvalene

KW - molecular building blocks

KW - electroactive organic material

U2 - 10.1039/C9TC00845D

DO - 10.1039/C9TC00845D

M3 - Article

VL - 7

SP - 6582

EP - 6591

JO - Journal of Materials Chemistry. C

JF - Journal of Materials Chemistry. C

SN - 2050-7526

IS - 22

ER -