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Phenylthiophene−Dipicolinic Acid-Based Emitters with Strong Solution Blue and Solid State Green Emission

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journal contribution
posted on 28.12.2006, 00:00 by Ana de Bettencourt-Dias, Andrei Poloukhtine
The synthesis and characterization of highly efficient blue emitting phenyl−thiophene compounds derivatized with dipicolinic acid bis(diethylamide) and dipicolinic acid diethyl ester 1, 2, and 3 are reported. Quantum yields were determined to be between 97% and 76% in methanol and 99% and 49% in toluene solution. The solvent dependences of the solution luminescence behavior are discussed in terms of solvent refractive index and dielectric constant as well as hydrogen-bonding capability. Luminescence is also observed in the solid state for the three compounds. A bathochromic shift in the emission wavelength is accompanied by solid-state quantum yields between 29% and 4%. HOMO and LUMO energies, in the range −5.55 to −5.71 eV and −2.20 to −2.48 eV, respectively, were determined experimentally from cyclic voltammetry and absorption spectroscopy experiments. The electrochemical characterization revealed that cyclic voltammetry can be utilized to deposit thin films of 3. An X-ray quality single crystal of 1 was isolated. This compound crystallizes in the monoclinic space group P21/c with cell parameters a = 15.224(3) Å, b = 8.9383(18) Å, c = 17.234(3) Å, β =114.36(3)°, and V = 2136.4(7) Å3. Appreciable solid state interactions in the form of π−π or S−S short contacts are not present, only weaker C−H···π. A large torsion angle of 30.28° between the phenyl and thiophene moieties and a small torsion angle of −3.37° between the pyridine and the thiophene moieties are seen.