Control of the association behavior by molecular design is one of the most essential benefits in artificial supramolecular systems. 1,14‐Dianilinotripyrrin has recently emerged as a novel conjugated molecule which forms a double helix in non‐polar solvents with the aid of multiple interstrand hydrogen bonding interactions. In this work, we investigated the substituent effects at the 5,10‐positions of tripyrrin on their association thermodynamics. This study illuminated two key findings; 1) electronic tuning by the para‐substituents reduce the entropic costs thereby slightly improve the association constants, and 2) ortho‐substituents force the tripyrrin core to be relatively planar, which significantly decreases the association constant due to less feasible π‐stacking.

Dissymmetrical α,α’-disubstituted tripyrrins have been prepared by a modified synthetic protocol. Tripyrrin 2a bearing 3,5-bis(trifluoromethyl)phenyl and 4-methoxyphenyl moieties showed an anti-type dimer arrangement in the solid-state. In contrast, syn-type dimers...

Control of the association behavior by the molecular design is one of the most essential benefits in artificial supramolecular systems. 1,14-Dianilinotripyrrin has recently emerged as a novel conjugated molecule which forms a double helix in non-polar solvents with the aid of multiple interstrand hydrogen bonding interactions. In this work, we investigated the substituent effects at the 5,10-positions of tripyrrin on their association dynamics. This study illuminated two key findings; 1) electronic tuning by the para-substituents reduce the entropic costs thereby slightly improve the association constants, and 2) ortho-substituents force the tripyrrin core to be relatively planar, which significantly decrease the association constant due to less feasible π-stacking.

Control of the association behavior by the molecular design is one of the most essential benefits in artificial supramolecular systems. 1,14-Dianilinotripyrrin has recently emerged as a novel conjugated molecule which forms a double helix in non-polar solvents with the aid of multiple interstrand hydrogen bonding interactions. In this work, we investigated the substituent effects at the 5,10-positions of tripyrrin on their association dynamics. This study illuminated two key findings; 1) electronic tuning by the para-substituents reduce the entropic costs thereby slightly improve the association constants, and 2) ortho-substituents force the tripyrrin core to be relatively planar, which significantly decrease the association constant due to less feasible π-stacking.