Excited‐State Carrier Dynamics in Semiconducting Heterostructures from Self‐Sorted NIR Active Dyes

Abstract Heterostructures comprise two or more different semiconducting materials stacked either as co‐assemblies or self‐sorted based on their dynamics of aggregates. However, self‐sorting in heterostructures is rather significant in improving the short exciton diffusion length and charge separation. Despite small organic molecules being known for their self‐sorting nature, macrocyclic are hitherto unknown owing to unrestrained assemblies from extended π‐conjugated systems. Herein, two near infrared region (NIR) active molecules comprised of porphyrin appended D‐π‐D (1) and A‐π‐A (2) have been reported to show the self‐assembled 0D and 2D nanostructures via J‐aggregates. Interestingly, the mixture of 1 and 2 reveals self‐sorting at the molecular level promoting nanosphere and sheet structures which further rolled over to spheres through π–π stacking leading to core–shell type heterostructure. Consequently, electrical conductivity is 10 times higher than the individual assemblies due to excited state electron transfer from 1 to 2 in a mixture, confirmed by femto second‐transient absorption spectroscopy and electrochemical impedance spectroscopy. These results suggest that controlling the self‐sorted heterostructures fosters refining the electronic properties which pave the way for designing novel NIR‐absorbed molecules for organic solar cells (OSCs).