Synthesis and optoelectronic properties of new ethynylated pyrazine derivatives

Several diaryleneethynylpyrazine derivatives, in which the pyrazine unit is electron-deficient, have been synthesised using Sonogashira palladium-catalysed cross-coupling reactions. Compound 32, an important intermediate in the synthesis of diaryleneethynylpyrazine derivatives was made by a modified literature procedure which improved the yield. Examination of optical absorption and photoluminescence spectra of compound 37 shows that the pyrazine unit does not change the behaviour significantly compared to analogue 42, while compound 38 shows pyridine substituents have a profound effect on the photophysics of these pyrazine systems. The redox properties of representative compound 37 were studied by cyclic voltammetry, which shows that reduction of 37 to its radical anion occurs as a reversible process at high negative potentials of ca. -1.87 V. The X-ray crystal structure of 37 is also presented. Quantum mechanical calculations of the geometry and electronic structure were performed for compound 37; the known phenylene analogue 42 was calculated at the same level for comparison. The results show that the energies of both HOMO and LUMO orbitals of 37 are decreased compared to 42. The calculated value of the HOMO-LUMO gap of 37 (3.56 eV) is close to that estimated from the red edge of the longest wavelength absorption (382 nm = 3.25 eV)