Toward New Electronic Structures in Crystallographically Ordered Conjugated Polymers

The polydiacetylenes1-3 (PDA, 1) are a class of conjugated polymers obtainable in crystallographically ordered form, a consequence of their synthesis via topochemical solid state polymerization. PDA have at least two physical properties, electronic carrier mobility and third-order nonlinear optical processes, whose coefficients have magnitudes reminiscent of prototypical atomic inorganic semiconductors.4 Current quantum chemical treatments5,6 are compatible with a description of PDA as broad-band one-dimensional semiconductors.