TY - JOUR
T1 - A Molecular Strategy to Lock-in the Conformation of a Perylene Bisimide-Derived Supramolecular Polymer
AU - Ashcraft, Adam
AU - Liu, Kaixuan
AU - Mukhopadhyay, Arindam
AU - Paulino, Victor
AU - Liu, Chuan
AU - Bernard, Brianna
AU - Husainy, Dalia
AU - Phan, Tina
AU - Olivier, Jean Hubert
PY - 2020/5/4
Y1 - 2020/5/4
N2 - Locking-in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)-derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable-temperature ground-state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non-covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid-state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non-covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100-mV stabilization of the conduction band energy when compared to that recorded for the non-covalent assembly.
AB - Locking-in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)-derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable-temperature ground-state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non-covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid-state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non-covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100-mV stabilization of the conduction band energy when compared to that recorded for the non-covalent assembly.
KW - electrochemistry
KW - excitonic properties
KW - perylene bisimide
KW - semiconducting nanomaterials
KW - supramolecular polymer
UR - http://www.scopus.com/inward/record.url?scp=85081357709&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85081357709&partnerID=8YFLogxK
U2 - 10.1002/anie.201911780
DO - 10.1002/anie.201911780
M3 - Article
C2 - 31984605
AN - SCOPUS:85081357709
VL - 59
SP - 7487
EP - 7493
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 19
ER -