title: Regiospecific formation and unusual optical properties of 2,5-bis(arylethynyl)rhodacyclopentadienes: a new class of luminescent organometallics.
abstract: A series of 2,5-bis(arylethynyl)rhodacyclopentadienes has been prepared by a rare example of regiospecific reductive coupling of 1,4-(p-R-phenyl)-1,3-butadiynes (R=H, Me, OMe, SMe, NMe2, CF3, CO2Me, CN, NO2, -C≡C-(p-C6H4-NHex2), -C≡C-(p-C6H4-CO2Oct)) at [RhX(PMe3)4] (1) (X=-C≡C-SiMe3 (a), -C≡C-(p-C6H4-NMe2) (b), -C≡C-C≡C-(p-C6H4-NPh2) (c) or -C≡C-{p-C6H4-C≡C-(p-C6H4 -N(C6H13)2)} (d) or Me (e)), giving the 2,5-bis(arylethynyl) isomer exclusively. The rhodacyclopentadienes bearing a methyl ligand in the equatorial plane (compound 1 e) have been converted into their chloro analogues by reaction with HCl etherate. The rhodacycles thus obtained are stable to air and moisture in the solid state and the acceptor-substituted compounds are even stable to air and moisture in solution. The photophysical properties of the rhodacyclopentadienes are highly unusual in that they exhibit, exclusively, fluorescence between 500-800 nm from the S1 state, with quantum yields of Φ=0.01-0.18 and short lifetimes (τ=0.45-8.20 ns). The triplet state formation (Φ(ISC) =0.57 for 2 a) is exceptionally slow, occurring on the nanosecond timescale. This is unexpected, because the Rh atom should normally facilitate intersystem crossing within femto- to picoseconds, leading to phosphorescence from the T1 state. This work therefore highlights that in some transition-metal complexes, the heavy atom can play a more subtle role in controlling the photophysical behavior than is commonly appreciated.
authors.affiliation: Institut für Anorganische Chemie, Julius Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany); Department of Chemistry, Durham University, South Road, Durham, DH1 3LE (UK).
authors.forename: Andreas
authors.initials: A
authors.lastname: Steffen
authors.forename: Richard M
authors.initials: RM
authors.lastname: Ward
authors.forename: Meng Guan
authors.initials: MG
authors.lastname: Tay
authors.forename: Robert M
authors.initials: RM
authors.lastname: Edkins
authors.forename: Fabian
authors.initials: F
authors.lastname: Seeler
authors.forename: Magda
authors.initials: M
authors.lastname: van Leeuwen
authors.forename: Lars-Olof
authors.initials: LO
authors.lastname: Pålsson
authors.forename: Andrew
authors.initials: A
authors.lastname: Beeby
authors.forename: Andrei S
authors.initials: AS
authors.lastname: Batsanov
authors.forename: Judith A K
authors.initials: JA
authors.lastname: Howard
authors.forename: Todd B
authors.initials: TB
authors.lastname: Marder
keywords: fluorescence; metallacycles; rhodium; spin-orbit coupling; transition metals