Treatment of 3-(1-hexynyl)perylene with Co2(CO)8 resulted in the formation of the dinuclear cobalt complex [Co2(CO)6(μ-η(2)-C4H9C≡C-Per)] (Per = 3-perylenyl) (1). The perylene derivatives 3-(2,3,5,6-tetrafluorophenyl)perylene (PerC6F4H) and 3-(2,3,5,6-tetrafluorophenyl)-9(10)hexylperylene (C6-PerC6F4H) were prepared and used to synthesize [AuR(CN(t)Bu)] (R = PerC6F4 2a), [AuR(CN(C6H2)-3,4,5-(OC12H25)3)] (R = PerC6F4 (3a), R = C6-PerC6F4 (3b)), trans-[PdR(PR'3)2X] (R = PerC6F4, R' = Ph, X = I (4a)); (R = C6-PerC6F4, R' = Ph, X = I (4b)); (R = PerC6F4, R' = Et, X = I (5a)); (R = C6-PerC6F4, R' = Et, X = I (5b)); (R = PerC6F4, R' = Ph, X = NCS (6a)), and trans-[Pd(PerC6F4)(PEt3)2X] (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° (2a) and 77.75° (6a). No π-π 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 Å. DFT calculations were performed on the absorption spectra of representative PerC6F4Y (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 ~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.