Your browser doesn't support javascript.
loading
A Facile Molecular Machine: Optically Triggered Counterion Migration by Charge Transfer of Linear Donor-π-Acceptor Phosphonium Fluorophores.
Belyaev, Andrey; Cheng, Yu-Hsuan; Liu, Zong-Ying; Karttunen, Antti J; Chou, Pi-Tai; Koshevoy, Igor O.
Afiliação
  • Belyaev A; Department of Chemistry, University of Eastern Finland, Yliopistokatu 7, 80101, Joensuu, Finland.
  • Cheng YH; Department of Chemistry, National (Taiwan) University, Taipei, 106, Taiwan.
  • Liu ZY; Department of Chemistry, National (Taiwan) University, Taipei, 106, Taiwan.
  • Karttunen AJ; Department of Chemistry and Materials Science, Aalto-University, 00076, Aalto, Finland.
  • Chou PT; Department of Chemistry, National (Taiwan) University, Taipei, 106, Taiwan.
  • Koshevoy IO; Department of Chemistry, University of Eastern Finland, Yliopistokatu 7, 80101, Joensuu, Finland.
Angew Chem Int Ed Engl ; 58(38): 13456-13465, 2019 Sep 16.
Article em En | MEDLINE | ID: mdl-31291049
The D-π-A type phosphonium salts in which electron acceptor (A=-+ PR3 ) and donor (D=-NPh2 ) groups are linked by polarizable π-conjugated spacers show intense fluorescence that is classically ascribed to excited-state intramolecular charge transfer (ICT). Unexpectedly, salts with π=-(C6 H4 )n - and -(C10 H6 C6 H4 )- exhibit an unusual dual emission (F1 and F2 bands) in weakly polar or nonpolar solvents. Time-resolved fluorescence studies show a successive temporal evolution from the F1 to F2 emission, which can be rationalized by an ICT-driven counterion migration. Upon optically induced ICT, the counterions move from -+ PR3 to -NPh2 and back in the ground state, thus achieving an ion-transfer cycle. Increasing the solvent polarity makes the solvent stabilization dominant, and virtually stops the ion migration. Providing that either D or A has ionic character (by static ion-pair stabilization), the ICT-induced counterion migration should not be uncommon in weakly polar to nonpolar media, thereby providing a facile avenue for mimicking a photoinduced molecular machine-like motion.
Palavras-chave

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Ano de publicação: 2019 Tipo de documento: Article