Poly(pyrazinoquinoxaline)s: New n‐Type Conjugated Polymers That Exhibit Highly Reversible Reduction and High Electron Affinity

The pyrazinoquinoxaline-based conjugated polymers poly(2,7-diphenylpyrazino(2,3-g)quinoxaline-3,8-diyl-1,4-phenylene) (PZQP) and poly(2,7-diphenylpyrazino(2,3-g)quinoxaline-3,8-diyl-2,5-thiophene) (PZQT) have been synthesized and characterized. PZQP and PZQT have optical band gaps of 2.44 and 1.76 eV, respectively. Both polymers showed highly reversible electrochemical reduction, with an electron affinity of 3.6 eV for PZQP and 3.8 eV for PZQT. The electronic structures of PZQP, PZQT, and related poly(pyrazinoquinoxaline)s, were calculated by density functional theory and compared with the experimental results.