Intramolecular energy transfer in pyrene-bodipy molecular dyads and triads.
Molecules bearing a 4,4-difluoro-8-(aryl)-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (bodipy) core and 1-pyrenyl-1-phenyl-4-(1-ethynylpyrene), or 1-phenyl-4-[1-ethynyl-(6-ethynylpyrene)pyrene] units were constructed in a step-by-step procedure based on palladium(0)-promoted cross-coupling reactions with the required preconstructed modules. X-ray structures of single crystals reveal a twisted arrangement of the two chromophores. In one case, an almost perfect orthogonal arrangement is found. These dyes are strongly luminescent in solution and display rich electrochemistry in which all redox processes of the bodipy and pyrene fragments are clearly resolved. The absorption spectra indicate that the bodipy and pyrene chromophores are spectrally isolated, thereby inducing a large "virtual" Stokes shift. The latter is realised by efficient transfer of intramolecular excitation energy by the Förster dipole-dipole mechanism. The rate of energy transfer depends on the structure of the dual-dye system and decreases as the centre-to-centre separation increases. The energy transfer efficiency, however, exceeds 90 % in all cases. The linkage of two pyrene residues by an ethyne group leads to a decrease in the energy-transfer efficiency, with the two polycycles acting as a single chromophore. The directly linked bodipy-pyrene dual dye binds to DNA and operates as an efficient solar concentrator when dispersed in plastic.
Ziessel
Raymond
R
Laboratoire de Chimie Moléculaire, Ecole de Chimie, Polymères, Matériaux (ECPM), Université Louis Pasteur (ULP), 25 rue Becquerel, 67087 Strasbourg Cedex 02, France. ziessel@chimie.u-strasbg.fr
Goze
Christine
C
Ulrich
Gilles
G
Césario
Michèle
M
Retailleau
Pascal
P
Harriman
Anthony
A
Rostron
James P
JP
D001896:Boron Compounds / Q000737:chemistry*; D004735:Energy Transfer; D005456:Fluorescent Dyes / Q000737:chemistry*; D011721:Pyrenes / Q000737:chemistry*; D014961:X-Ray Diffraction
C095489:4,4-difluoro-4-bora-3a,4a-diaza-s-indacene; D001896:Boron Compounds; D005456:Fluorescent Dyes; D011721:Pyrenes; C030984:pyrene