Highly fluorescent complexes with gold, palladium or platinum linked to perylene through a tetrafluorophenyl group

Treatment of 3-(1-hexynyl) perylene with Co-2(CO)(8) resulted in the formation of the dinuclear cobalt complex [Co-2(CO)(6)(mu-eta(2)-C4H9C=C-Per)] (Per = 3-perylenyl) (1). The perylene derivatives 3-(2,3,5,6-tetrafluorophenyl) perylene (PerC(6)F(4)H) and 3-(2,3,5,6-tetrafluorophenyl)-9(10) hexylperylene (C-6-PerC(6)F(4)H) were prepared and used to synthesize [AuR(CNtBu)] (R = PerC(6)F(4) 2a), [AuR(CN(C6H2)-3,4,5-(OC12H25) 3)] (R = PerC(6)F(4) (3a), R = C-6-PerC(6)F(4) (3b)), trans-[PdR(PR'(3))(2)X] (R = PerC(6)F(4), R' = Ph, X = I (4a)); (R = C-6-PerC(6)F(4), R' = Ph, X = I (4b)); (R = PerC(6)F(4), R' = Et, X = I (5a)); (R = C-6-PerC(6)F(4), R' = Et, X = I (5b)); (R = PerC(6)F(4), R' = Ph, X = NCS (6a)), and trans-[Pd(PerC(6)F(4))(PEt3)(2)X] (X = Br (7a); X = I (8a)). The molecular structure of complexes 1, 2a, and 6a has been determined by X-ray diffraction analysis. The perylenyl fragments of complexes 2a or 6a are essentially planar and make dihedral angles to the tetrafluorophenyl plane of 57.49 degrees (2a) and 77.75 degrees (6a). No pi-pi stacking of perylenyl rings is observed in any of the three molecules, but 2a shows association of two monomers (arranged almost antiparallel), with an Au. Au distance of 3.114 angstrom. DFT calculations were performed on the absorption spectra of representative PerC(6)F(4)Y (Y = H, F, Au(CNMe), PtBr(PMe3)(2) and PdBr(PMe3)(2)). All complexes exhibit fluorescence associated with the perylene fragment with emission quantum yields, in solution at room temperature, in the range 0.20-0.90 and emission lifetimes similar to 4 ns, and no significant differences in the emission maxima, due to an efficient electronic decoupling of the metal fragment from the HOMO and LUMO of the perylene chromophore. The latter is confirmed by DFT calculations.