Premium
Intense Ground‐State Charge‐Transfer Interactions in Low‐Bandgap, Panchromatic Phthalocyanine–Tetracyanobuta‐1,3‐diene Conjugates
Author(s) -
Sekita Michael,
Ballesteros Beatriz,
Diederich François,
Guldi Dirk M.,
Bottari Giovanni,
Torres Tomás
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601258
Subject(s) - tetracyanoethylene , photochemistry , chemistry , excited state , diene , ground state , aniline , electron transfer , panchromatic film , cycloaddition , organic chemistry , catalysis , atomic physics , physics , natural rubber , image resolution , optics
A cycloaddition–retroelectrocyclization reaction between tetracyanoethylene and two zinc phthalocyanines (Zn II Pcs) bearing one or four anilino‐substituted alkynes has been used to install a strong, electron‐accepting tetracyanobuta‐1,3‐diene (TCBD) between the electron‐rich Zn II Pc and aniline moieties. A combination of photophysical, electrochemical, and spectroelectrochemical investigations with the Zn II Pc‐TCBD‐aniline conjugates, which present panchromatic absorptions in the visible region extending all the way to the near infrared, show that the formal replacement of the triple bond by TCBD has a dramatic effect on their ground‐ and excited‐state features. In particular, the formation of extremely intense, ground‐state charge‐transfer interactions between Zn II Pc and the electron‐accepting TCBD were observed, something unprecedented not only in Pc chemistry but also in TCBD‐based porphyrinoid systems.