The branching topology of end groups attached to several series of oligothiophenes has a systematic effect on thermal and electrical properties of the oligomers. The series were synthesized in a modular approach and show a distinct drop of the melting point T m on increasing bulkiness of the substituents. The same trend can be found for the dissociation temperatures T dis of aggregates in solution. Similarly, monolayer OFET mobilities μ FET are significantly decreasing with increasing bulkiness of the substituents. A simple geometric model is presented quantitatively correlating the transition temperatures and mobilities with the substituents' structure based on a bulkiness parameter P, which allows predicting T m , T dis , and μ FET of corresponding not yet synthesized oligomers with branched substituents. This model might be generally applicable for endcapped rod-like conjugated oligomers.
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