title: Intense Ground-State Charge-Transfer Interactions in Low-Bandgap, Panchromatic Phthalocyanine-Tetracyanobuta-1,3-diene Conjugates.
abstract: 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.
authors.affiliation: Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058, Erlangen, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Sekita
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain.|IMDEA-Nanociencia, c/Faraday 9, Campus de Cantoblanco, 28049, Madrid, Spain.
authors.forename: Beatriz
authors.initials: B
authors.lastname: Ballesteros
authors.affiliation: Laboratory of Organic Chemistry, ETH Zurich, Vladimir-Prelog-Weg 3, 8093, Zurich, Switzerland.
authors.forename: François
authors.initials: F
authors.lastname: Diederich
authors.affiliation: Department of Chemistry and Pharmacy, Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058, Erlangen, Germany. dirk.guldi@fau.de.
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain. giovanni.bottari@uam.es.|IMDEA-Nanociencia, c/Faraday 9, Campus de Cantoblanco, 28049, Madrid, Spain. giovanni.bottari@uam.es.
authors.forename: Giovanni
authors.identifier: 0000-0001-6141-7027
authors.initials: G
authors.lastname: Bottari
authors.affiliation: Departamento de Química Orgánica, Universidad Autónoma de Madrid, Campus de Cantoblanco, 28049, Madrid, Spain. tomas.torres@uam.es.|IMDEA-Nanociencia, c/Faraday 9, Campus de Cantoblanco, 28049, Madrid, Spain. tomas.torres@uam.es.
authors.forename: Tomás
authors.identifier: 0000-0001-9335-6935
authors.initials: T
authors.lastname: Torres
keywords: charge transfer; donor-acceptor systems; photophysics; phthalocyanines; tetracyanobutadienes