Toward Redox-Active Indenofluorene-Extended Tetrathiafulvalene Oligomers-Synthesis and Studies of Dimeric Scaffolds
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Toward Redox-Active Indenofluorene-Extended Tetrathiafulvalene Oligomers-Synthesis and Studies of Dimeric Scaffolds. / Broløs, Line; Kilde, Martin Drøhse; Hammerich, Ole; Nielsen, Mogens Brøndsted.
I: The Journal of Organic Chemistry, Bind 85, Nr. 5, 06.03.2020, s. 3277-3286.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Toward Redox-Active Indenofluorene-Extended Tetrathiafulvalene Oligomers-Synthesis and Studies of Dimeric Scaffolds
AU - Broløs, Line
AU - Kilde, Martin Drøhse
AU - Hammerich, Ole
AU - Nielsen, Mogens Brøndsted
PY - 2020/3/6
Y1 - 2020/3/6
N2 - The promotion of mixed-valence interactions between redox-active, π-conjugated scaffolds is of interest when developing new conducting or electrochromic materials as well as in the construction of redox-controlled supramolecular assemblies. In this work, dimeric structures of the redox-active indenofluorene-extended tetrathiafulvalene (IF-TTF) unit were synthesized in a stepwise protocol. The synthesis relied on the development of a new unsymmetrical IF-TTF building block by a combination of phosphite-mediated and Horner-Wadsworth-Emmons reactions for introduction of the dithiafulvene units. The redox properties were studied by cyclic voltammetry, where it was observed that a first one-electron oxidation, corresponding to a mixed-valence state, occurs at a significantly lower potential when the IF-TTF unit is incorporated into a dimer, compared to a monomer analogue. This result indicates that locking the redox-active IF-TTF units in close proximity promotes intramolecular mixed-valence interactions. A computational study was also conducted, supporting the involvement of intramolecular interactions.
AB - The promotion of mixed-valence interactions between redox-active, π-conjugated scaffolds is of interest when developing new conducting or electrochromic materials as well as in the construction of redox-controlled supramolecular assemblies. In this work, dimeric structures of the redox-active indenofluorene-extended tetrathiafulvalene (IF-TTF) unit were synthesized in a stepwise protocol. The synthesis relied on the development of a new unsymmetrical IF-TTF building block by a combination of phosphite-mediated and Horner-Wadsworth-Emmons reactions for introduction of the dithiafulvene units. The redox properties were studied by cyclic voltammetry, where it was observed that a first one-electron oxidation, corresponding to a mixed-valence state, occurs at a significantly lower potential when the IF-TTF unit is incorporated into a dimer, compared to a monomer analogue. This result indicates that locking the redox-active IF-TTF units in close proximity promotes intramolecular mixed-valence interactions. A computational study was also conducted, supporting the involvement of intramolecular interactions.
U2 - 10.1021/acs.joc.9b03118
DO - 10.1021/acs.joc.9b03118
M3 - Journal article
C2 - 31984743
VL - 85
SP - 3277
EP - 3286
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
SN - 0022-3263
IS - 5
ER -
ID: 243197287