Kelly Gaffney, Postdoctoral Faculty Sponsor
- Singlet Fission in Terrylenediimide Single Crystals: Competition between Biexciton Annihilation and Free Triplet Exciton Formation JOURNAL OF PHYSICAL CHEMISTRY C 2021; 125 (25): 13946-13953
Growth of Extra-Large Chromophore Supramolecular Polymers for Enhanced Hydrogen Production
2021; 21 (9): 3745-3752
The control of morphology in bioinspired chromophore assemblies is key to the rational design of functional materials for light harvesting. We investigate here morphological changes in perylene monoimide chromophore assemblies during thermal annealing in aqueous environments of high ionic strength to screen electrostatic repulsion. We found that annealing under these conditions leads to the growth of extra-large ribbon-shaped crystalline supramolecular polymers of widths from about 100 nm to several micrometers and lengths from 1 to 10 μm while still maintaining a unimolecular thickness. This growth process was monitored by variable-temperature absorbance spectroscopy, synchrotron X-ray scattering, and confocal microscopy. The extra-large single-crystal-like supramolecular polymers are highly porogenic, thus creating loosely packed hydrogel scaffolds that showed greatly enhanced photocatalytic hydrogen production with turnover numbers as high as 13 500 over ∼110 h compared to 7500 when smaller polymers are used. Our results indicate great functional opportunities in thermally and pathway-controlled supramolecular polymerization.
View details for DOI 10.1021/acs.nanolett.0c05024
View details for Web of Science ID 000651773600006
View details for PubMedID 33877843