The first regiochemical analysis of self-doped polythiophenes is prese
nted. Regioregularity is as signed based on the H-1 and C-13 NMR spect
ra of sodium poly(3-(3-thienyl)propanesulfonate) (1) and sodium poly(6
-(3-thienyl)hexanesulfonate) (2) to particular configurational diads a
nd triads, using one-and two-dimensional nuclear Overhauser effect (NO
E), double quantum filtered homonuclear correlational spectroscopy (DQ
F-COSY), and heteronuclear multiple-quantum coherence (HMQC) experimen
ts. Excellent resolution enhancement of peaks is obtained with a Gauss
ian multiplication. An estimate of the relative populations of the con
figurational triads in these polymers is thereby obtained. The ratio o
f HT to HH diads in both 1 and 2 is 4:1, based on the areas associated
with the aromatic NMR signals.