%0 Generic
%A Jayamurugan, Govindasamy
%A Dumele, Oliver
%A Gisselbrecht, Jean-Paul
%A Boudon, Corinne
%A Schweizer, W. Bernd
%A Bernet, Bruno
%A Diederich, François
%D 2016
%T Expanding the Chemical Structure Space of Opto-Electronic
Molecular Materials: Unprecedented Push–Pull Chromophores by
Reaction of a Donor-Substituted Tetracyanofulvene with Electron-Rich
Alkynes
%U https://acs.figshare.com/articles/dataset/Expanding_the_Chemical_Structure_Space_of_Opto_Electronic_Molecular_Materials_Unprecedented_Push_Pull_Chromophores_by_Reaction_of_a_Donor_Substituted_Tetracyanofulvene_with_Electron_Rich_Alkynes/2437144
%R 10.1021/ja312084s.s002
%2 https://acs.figshare.com/ndownloader/files/4079698
%K chromophore
%K pentafulvenes feature
%K cycloaddition
%K bi
%K structure elucidation
%K ring opening
%K TCPF
%K electronics devices
%K Chemical Structure Space
%K chiral cyclobutenylated tetrahydropentalene
%K pentafulvenes show
%K absorption bands
%X The reaction of a 3,5-bis(N,N-dimethylanilino)-substituted 2,4,6,6-tetracyanopentafulvene
(TCPF)
with mono- and bis(N,N-dimethylanilino)acetylene
provides facile access to push–pull chromophores with diverse
new scaffolds. The starting TCPF reacts with bis(N,N-dimethylanilino)acetylene in a formal [2+2] cycloaddition
at the exocyclic double bond, followed by retroelectrocyclization,
to yield an ethenylene-extended push–pull pentafulvene. The
transformation with 4-ethynyl-N,N-dimethylaniline also yields a similar extended pentafulvene as well
as two other products that required X-ray analysis for their structure
elucidation. One features an 8,8-dicyanoheptafulvene core formed by
formal [2+2] cycloaddition, followed by ring opening via fragmentation.
The second is a chiral cyclobutenylated tetrahydropentalene, resulting
from a cascade of formal [6+2] and [2+2] cycloadditions. All new nonplanar
push–pull chromophores display amphoteric redox behavior with
both strong electron-donating and -accepting potency. Notably, the N,N-dimethylanilino-substituted extended
pentafulvenes show remarkably low oxidation potentials (0.27/0.28
V vs Fc/Fc+ reference) that are lower than those for N,N-dimethylaniline itself. The push–pull-substituted
extended pentafulvenes feature intense electronic absorption bands,
extending over the entire visible spectral range into the near infrared,
and low highest occupied molecular orbital–lowest unoccupied
molecular orbital gaps. These properties, together with high thermal
stability and good solubility, suggest the potential use of the new
chromophores as advanced materials in molecular electronics devices.
%I ACS Publications