The charged states of the conjugated polymers poly(2-methoxy,5-(2′-ethylhexyloxy)-p- phenylenevinylene) (MEH-PPV) and poly(2,5-pyridinediyl) (PPY) have been studied by pulse radiolysis. Following pulse radiolysis of argon-saturated solutions of MEH-PPV in chloroform, a new absorption is seen to grow in over a few hundred microseconds. This has a principal absorption at 1.43 eV and a weaker, low energy band (⩽0.80 eV), and is assigned to the positive one-electron charge state (positive polaron) of MEH-PPV. The slow absorption decay is unaffected by oxygen. Negative charge states (negative polarons), with absorptions around 1.4 eV, are produced upon pulse radiolysis of MEH-PPV in argon-saturated solutions in tetrahydrofuran (THF) or benzonitrile. A small solvatochromic shift is observed. In contrast to the behavior of the positive polaron, the MEH-PPV negative charge carriers decay fairly rapidly, and are readily quenched by molecular oxygen. Previous results on chemically produced positive and negative charge states of conjugated polymers and oligomers are discussed on the basis of these assignments, and comparison is made with theoretical calculations. Using benzophenone as a charge scavenger, pulse radiolysis of formic acid is shown to generate one-electron reducing species. Various derivatives of PPY, including a regioregular polymer (rPPY) and a hexyl substituted compound (HPPY) have been studied by pulse radiolysis in formic acid solution. With rPPY, new absorptions are observed at 2.59 and 1.40 eV, and are assigned to the one-electron reduced species. These are strongly quenched by molecular oxygen. With HPPY, the lower energy transition is broadened to give a maximum below 1.21 eV and a shoulder at 1.65 eV. The differences between rPPY and HPPY are interpreted on the basis of differences in the rigidity of the polymer. The relevance of these assignments to the identification of charged species in photoinduced absorption measurements is indicated.
