title: Sensitisation of Eu(III)- and Tb(III)-based luminescence by Ir(III) units in Ir/lanthanide dyads: evidence for parallel energy-transfer and electron-transfer based mechanisms.
abstract: A series of blue-luminescent Ir(III) complexes with a pendant binding site for lanthanide(III) ions has been synthesized and used to prepare Ir(III)/Ln(III) dyads (Ln = Eu, Tb, Gd). Photophysical studies were used to establish mechanisms of Ir→Ln (Ln = Tb, Eu) energy-transfer. In the Ir/Gd dyads, where direct Ir→Gd energy-transfer is not possible, significant quenching of Ir-based luminescence nonetheless occurred; this can be ascribed to photoinduced electron-transfer from the photo-excited Ir unit (*Ir, (3)MLCT/(3)LC excited state) to the pendant pyrazolyl-pyridine site which becomes a good electron-acceptor when coordinated to an electropositive Gd(III) centre. This electron transfer quenches the Ir-based luminescence, leading to formation of a charge-separated {Ir(4+)}˙-(pyrazolyl-pyridine)˙(-) state, which is short-lived possibly due to fast back electron-transfer (<20 ns). In the Ir/Tb and Ir/Eu dyads this electron-transfer pathway is again operative and leads to sensitisation of Eu-based and Tb-based emission using the energy liberated from the back electron-transfer process. In addition direct Dexter-type Ir→Ln (Ln = Tb, Eu) energy-transfer occurs on a similar timescale, meaning that there are two parallel mechanisms by which excitation energy can be transferred from *Ir to the Eu/Tb centre. Time-resolved luminescence measurements on the sensitised Eu-based emission showed both fast and slow rise-time components, associated with the PET-based and Dexter-based energy-transfer mechanisms respectively. In the Ir/Tb dyads, the Ir→Tb energy-transfer is only just thermodynamically favourable, leading to rapid Tb→Ir thermally-activated back energy-transfer and non-radiative deactivation to an extent that depends on the precise energy gap between the *Ir and Tb-based (5)D4 states. Thus, the sensitised Tb(iii)-based emission is weak and unusually short-lived due to back energy transfer, but nonetheless represents rare examples of Tb(III) sensitisation by a energy donor that could be excited using visible light as opposed to the usually required UV excitation.
authors.affiliation: Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK. m.d.ward@sheffield.ac.uk.
authors.forename: Daniel
authors.initials: D
authors.lastname: Sykes
authors.forename: Ahmet J
authors.initials: AJ
authors.lastname: Cankut
authors.forename: Noorshida Mohd
authors.initials: NM
authors.lastname: Ali
authors.forename: Andrew
authors.initials: A
authors.lastname: Stephenson
authors.forename: Steven J P
authors.initials: SJ
authors.lastname: Spall
authors.forename: Simon C
authors.initials: SC
authors.lastname: Parker
authors.forename: Julia A
authors.initials: JA
authors.lastname: Weinstein
authors.forename: Michael D
authors.initials: MD
authors.lastname: Ward