Thiophene-containing heteroarenes are one of the most well-known classes of π-conjugated building blocks for photoactive molecules. Isomeric naphthodithiophenes (NDTs) are at the forefront of this research area due to their straightforward synthesis and derivatization. Notably, NDT geometries that are bent - such as naphtho[2,1-b:3,4-b']dithiophene (α-NDT) and naphtho[1,2-b:4,3-b']dithiophene (β-NDT) - are seldom employed as photoactive small molecules. This report investigates how remote substituents impact the photophysical properties of isomeric α- and β-NDTs. The orientation of the thiophene units plays a critical role in the emission: in the α(OHex)R2 series conjugation from the end-caps to the NDT core is apparent, while in the β(Oi-Pent)R2 series minimal change is observed unless strong electron acceptors, such as β(Oi-Pent)(PhCF3)2, are employed. This push-pull acceptor-donor-acceptor (A-D-A) fluorophore exhibits positive fluorosolvatochromism that correlates with increasing solvent polarity parameter, E T(30). In total, these results highlight how remote substituents are able to modulate the emission of isomeric bent NDTs.
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