Highly fluorescent complexes with 3-isocyanoperylene and N-(2,5-di-tert-butylphenyl)-9-isocyano-perylene-3,4-dicarboximide

Abstract

Perylenyl isocyanide metal complexes exhibit a high perylene based fluorescence modified by weak electronic interaction of the metal and the perylene orbitals.

Higher fluorescence in platinum(iv) orthometallated complexes of perylene imine compared with their platinum(ii) or palladium(ii) analogues

“…We have reported also high fluorescence properties perylene derivatives with gold, palladium or platinum complex fragments attached to perylene through a tetrafluorophenyl linker, associated to the fact that the π--systems of the perylene and tetrafluorophenyl fragments are uncoupled; 4 or with an isocyanide group acts as a connector between a Au, Pd, Cr, Mo, W complex fragments and the perylene chromophore, for which theoretical calculations indicate a very weak interactions of the metal with the π--system of the perylene. 5 A different possibility to build metal derivatives bearing perylene fragment has been the functionalization of perylene with an imine group. Using Pd derivatives, our group reported the first examples of five or six--membered metallacyclic complexes derived from the 3--perilenylmethylen--4'--ethylaniline ligand, with two different bonding modes to Pd II derived from the two possible metallation sites of the 3--substituded perylene.…”

Fluorescent perylenylpyridine complexes: an experimental and theoretical study

“…6 (calculated values for perylene are 442 and 257 nm, respectively). 13 These two absorptions are characteristic of all the perylene derivatives, 6a,6b,12,13, 17 ,20 and can be found in all the spectra, although modified in energy. Interestingly, the six-membered-cyclometallated complex [Pd(PerPy)(acac)] (5) shows in the calculations a clear red shift to 534 nm of the HOMO  LUMO transition.…”

“…The most intense, at 465 nm, is experimentally observed in chloroform solution very close to the calculated value (Table 2), and corresponds to a HOMO  LUMO transition. 6a, 12,13 Both orbitals are centred in the perylene -system (94 and 91%, respectively). A second peak is expected at 261 nm, composed by different single monoexcitations between  systems of the perylene, in particular between the HOMO and the higher  empty orbital in Fig.…”

“…Using this approach, we have reported before highly fluorescent perylene derivatives with Au, Pd or Pt complex fragments attached to perylene through a tetrafluorophenyl linker, 12 or complexes with an isocyanide group acting as the connector between Au, Pd, Cr, Mo, W complex fragments and the perylene chromophore. 13 In both cases, the perylene electron density is weakly influenced by the substituents in the ring and by the metal fragments. In contrast, ethynyl-substituted perylene or perylene monoimide Pt II complexes are not emissive, but readily sensitize 1 O 2 due to the population of the perylene centred triplet excited state.…”

Tuning the luminescence of transition metal complexes with acyclic diaminocarbene ligands

“…116 and 117 with the perylene substituents at the periphery were obtained by the nucleophilic attack of NHEt 2 on the Au i -bound perylene isocyanide in 114 and 115 (Scheme 18). 156 The UV-Vis absorption profiles of 114–117 are similar and dominated by the π–π* transition inside of the perylene moiety. The absorption maxima of 116 and 117 at 450 nm are blueshifted ( Δ = 990 cm −1 ) from the parent isocyanides 114 and 115 and redshifted ( Δ = 550 cm −1 ) from free perylene.…”