Intermolecular Interactions in π-Stacked Conjugated Molecules. Synthesis, Structure, and Spectral Characterization of Alkyl Bithiazole Oligomers

Syntheses are reported of new 4,4‘-dialkyl-2,2‘-bithiazole oligomers that have alkenoxy side chains
that are capable of easy conversion to oligomers with functionalized side chains, e.g., terminally substituted
hydroxy chains. The crystal structures of two representative oligomers (4,4‘,4‘ ‘,4‘ ‘‘-tetra-(2-propenoxymethyl)-2,2‘,5‘,5‘ ‘,2‘ ‘,2‘ ‘‘-quaterthiazole (3P2) and 4,4‘,4‘ ‘,4‘ ‘‘-tetra-(3-hydroxypropyloxymethyl)-2,2‘,5‘,5‘ ‘,2‘ ‘,2‘ ‘‘-quaterthiazole (3H2)) were determined; 3P2 crystallizes in a π-stacked motif with two molecules per unit
cell, whereas 3H2 forms π-stacks that are linked with hydrogen bonds to form infinite two-dimensional
sheets with one molecule per unit cell. A comparison of the UV−vis spectra of the compounds in solution
and in the solid state provides unequivocal evidence for the presence of a Davydov splitting, WD ≈ 0.2 eV,
in solid 3P2. The spectra are interpreted in the framework of molecular exciton theory to extract a value of
the intermolecular transfer integral, J ≈ 0.2 eV, for a total exciton bandwidth of ca. 0.8 eV. Monte Carlo
calculations were used to determine the density of states of the exciton band and the absorption and emission
line shapes of the 0 ← 0 transition. It is suggested that the “three-humped” absorption profile typical of
partially crystalline, regioregular polymers is the “optical signature” of π-stacking.