Convenient synthesis and polymerization of 5,6‐disubstituted dithiophthalides toward soluble poly(isothianaphthene): An initial spectroscopic characterization of the resulting low‐band‐gap polymers

A new synthetic procedure toward substituted dithiophthalides, 5,6‐dialkyloxydithiophthalide and 5,6‐dithioalkyldithiophthalide, is presented. 5,6‐Dithiooctyldithiophthalide was obtained from 4,5‐dichlorophthalic acid in an eight‐step reaction with an overall yield of 26%. 5,6‐Dioctyloxydithiophthalide was obtained from 4,5‐dihydroxyphthalic acid dimethyl ester in a seven‐step reaction (overall yield = 15%). Both monomers were polymerized by a thermal and nonoxidative polymerization that resulted in soluble poly(isothianaphthene) derivatives with a band gap of about 1.2 eV. Photoinduced absorption measurements revealed the existence of charged excitations upon illumination. The photoinduced charge generation, combined with the extensive light‐harvesting properties and the easy processability, makes these materials quite promising for photovoltaic applications.