Tunable electronic interactions between anions and perylenediimide.
Org Biomol Chem
; 11(29): 4797-803, 2013 Aug 07.
Article
em En
| MEDLINE
| ID: mdl-23778991
ABSTRACT
Over the past decade anion-π interaction has emerged as a new paradigm of supramolecular chemistry of anions. Taking advantage of the electronic nature of anion-π interaction, we have expanded its boundaries to charge-transfer (CT) and formal electron transfer (ET) events by adjusting the electron-donating and accepting abilities of anions and π-acids, respectively. To establish that ET, CT, and anion-π interactions could take place between different anions and π-acids as long as their electronic and structural properties are conducive, herein, we introduce 3,4,9,10-perylenediimide (PDI-1) that selectively undergoes thermal ET from strong Lewis basic hydroxide and fluoride anions, but remains electronically and optically silent to poor Lewis basic anions, as ET and CT events are turned OFF. These interactions have been fully characterized by UV/Vis, NMR, and EPR spectroscopies. These results demonstrate the generality of anion-induced ET events in aprotic solvents and further refute a notion that strong Lewis basic hydroxide and fluoride ions can only trigger nucleophilic attack to form covalent bonds instead of acting as sacrificial electron donors to π-acids under appropriate conditions.
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01-internacional
Base de dados:
MEDLINE
Assunto principal:
Perileno
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Imidas
Idioma:
En
Revista:
Org Biomol Chem
Ano de publicação:
2013
Tipo de documento:
Article