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Fulvalene‐Based Polycyclic Aromatic Hydrocarbon Ladder‐Type Structures: Synthesis and Properties
Author(s) -
Bliksted Roug Pedersen Viktor,
Granhøj Jeppe,
Erbs HillersBendtsen Andreas,
Kadziola Anders,
Mikkelsen Kurt V.,
Brøndsted Nielsen Mogens
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100984
Subject(s) - reagent , conjugated system , polycyclic aromatic hydrocarbon , chemistry , graphene , redox , homo/lumo , hydrocarbon , electrochemistry , electronic structure , photochemistry , materials science , molecule , organic chemistry , computational chemistry , nanotechnology , polymer , electrode
Polycyclic aromatic hydrocarbons (PAHs) have found strong interest for their electronic properties and as model systems for graphene. While PAHs have been studied intensively as single units, here PAHs were constructed in ladder‐type arrangements using cross‐conjugated fulvalene and dithiafulvalene motifs as connecting units and moving forward a convenient synthetic approach for dimerizing (thio)ketones into olefins by the action of Lawesson's reagent. Some of the PAHs can also be regarded as “super‐extended” tetrathiafulvalenes (TTFs) with some of the largest cores ever explored, being multi‐redox systems that exhibit both reversible oxidations and reductions. Concomitant absorption redshifts were observed when expanding the ladder‐type structures from one to two to three indenofluorene units, and optical and electrochemical HOMO‐LUMO gaps were found to correlate linearly. Various conformations (and solid‐state packing arrangements) were studied by X‐ray crystallography and computations.