Abstract
The spontaneous self-assembly of chromophores into light-harvesting antennae provides a potentially low-cost approach to building solar-to-fuel conversion materials. However, designing such supramolecular architectures requires a better understanding of the balance between noncovalent forces among the molecular components. We investigated here the aqueous assembly of perylene monoimide chromophore amphiphiles synthesized with different substituents in the 9-position. The molecular dipole strength decreases as the nature of the substituent is altered from electron donating to electron withdrawing. Compounds with stronger molecular dipoles, in which dipolar interactions stabilize assemblies by 10-15 kJ·mol-1, were found to form crystalline nanoribbons in solution. In contrast, when the molecular dipole moment is small, nanofibers were obtained. Highly blue-shifted absorption maxima were observed in assemblies with large dipoles, indicating strong electronic coupling is present. However, only the moderate dipole compound had the appropriate molecular packing to access charge-transfer excitons leading to enhanced photocatalytic H2 production.
| Original language | English |
|---|---|
| Pages (from-to) | 4965-4968 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 140 |
| Issue number | 15 |
| DOIs | |
| Publication status | Published - Apr 18 2018 |
Fingerprint
ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Chromophore Dipole Directs Morphology and Photocatalytic Hydrogen Generation. / Weingarten, Adam S.; Dannenhoffer, Adam J.; Kazantsev, Roman V.; Sai, Hiroaki; Huang, Dongxu; Stupp, Samuel I.
In: Journal of the American Chemical Society, Vol. 140, No. 15, 18.04.2018, p. 4965-4968.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Chromophore Dipole Directs Morphology and Photocatalytic Hydrogen Generation
AU - Weingarten, Adam S.
AU - Dannenhoffer, Adam J.
AU - Kazantsev, Roman V.
AU - Sai, Hiroaki
AU - Huang, Dongxu
AU - Stupp, Samuel I
PY - 2018/4/18
Y1 - 2018/4/18
N2 - The spontaneous self-assembly of chromophores into light-harvesting antennae provides a potentially low-cost approach to building solar-to-fuel conversion materials. However, designing such supramolecular architectures requires a better understanding of the balance between noncovalent forces among the molecular components. We investigated here the aqueous assembly of perylene monoimide chromophore amphiphiles synthesized with different substituents in the 9-position. The molecular dipole strength decreases as the nature of the substituent is altered from electron donating to electron withdrawing. Compounds with stronger molecular dipoles, in which dipolar interactions stabilize assemblies by 10-15 kJ·mol-1, were found to form crystalline nanoribbons in solution. In contrast, when the molecular dipole moment is small, nanofibers were obtained. Highly blue-shifted absorption maxima were observed in assemblies with large dipoles, indicating strong electronic coupling is present. However, only the moderate dipole compound had the appropriate molecular packing to access charge-transfer excitons leading to enhanced photocatalytic H2 production.
AB - The spontaneous self-assembly of chromophores into light-harvesting antennae provides a potentially low-cost approach to building solar-to-fuel conversion materials. However, designing such supramolecular architectures requires a better understanding of the balance between noncovalent forces among the molecular components. We investigated here the aqueous assembly of perylene monoimide chromophore amphiphiles synthesized with different substituents in the 9-position. The molecular dipole strength decreases as the nature of the substituent is altered from electron donating to electron withdrawing. Compounds with stronger molecular dipoles, in which dipolar interactions stabilize assemblies by 10-15 kJ·mol-1, were found to form crystalline nanoribbons in solution. In contrast, when the molecular dipole moment is small, nanofibers were obtained. Highly blue-shifted absorption maxima were observed in assemblies with large dipoles, indicating strong electronic coupling is present. However, only the moderate dipole compound had the appropriate molecular packing to access charge-transfer excitons leading to enhanced photocatalytic H2 production.
UR - http://www.scopus.com/inward/record.url?scp=85045560551&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85045560551&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b12641
DO - 10.1021/jacs.7b12641
M3 - Article
VL - 140
SP - 4965
EP - 4968
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 15
ER -