TY - JOUR
T1 - Polymorphism and Optoelectronic Properties in Crystalline Supramolecular Polymers
AU - Grabicki, Niklas
AU - Dumele, Oliver
AU - Sai, Hiroaki
AU - Powers-Riggs, Natalia E.
AU - Phelan, Brian T.
AU - Sangji, M. Hussain
AU - Chapman, Craig T.
AU - Passarelli, James V.
AU - Dannenhoffer, Adam J.
AU - Wasielewski, Michael R.
AU - Stupp, Samuel I.
N1 - Funding Information:
Use of the Advanced Photon Source (APS) was supported by the Basic Energy Sciences program of the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. Angle dependent X-ray experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the APS. DND-CAT is supported by Northwestern University, E.I. DuPont de Nemours & Co., and the Dow Chemical Company. We thank the Biological Imaging Facility at Northwestern for the use of TEM equipment and the Electron Probe Instrumentation Center facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental Center for the use of TEM and SEM. NMR and mass spectroscopy equipment at the Integrated Molecular Structure Education and Research Center was supported by the National Science Foundation under CHE-9871268. We would like to thank Mark Seniw for the preparation of the morphology graphics.
Funding Information:
This work was primarily supported by the Center for Bio-Inspired Energy Science (CBES), an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences, under Award No. DE-SC0000989. Additional support for the time-resolved spectroscopy was provided by the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the Basic Energy Sciences program of the U.S. Department of Energy Office of Science under Award No. DE-SC0001059. N.E.P.-R. was supported by NSF Graduate Research Fellowship (DGE-1324585). N.G. was supported by a PROMOS scholarship of the German Academic Exchange Service (DAAD) and the Humboldt University Berlin. O.D. acknowledges funding by the Swiss National Science Foundation (SNF, Project P2EZP2_168881) via an Early Postdoc.Mobility fellowship and the National Academy of Sciences Leopoldina (Germany) for a postdoctoral fellowship (LPDS 2016-4).
Publisher Copyright:
©
PY - 2021/1/26
Y1 - 2021/1/26
N2 - Supramolecular polymers can emulate some of the physical properties of covalent polymers but offer new opportunities given the possibility of designing monomers that will form highly ordered assemblies with defined shapes. Internally ordered supramolecular polymers formed through nucleation-elongation self-assembly are well-known but highly crystalline examples which exhibit important properties such as light harvesting, charge transport, and ferroelectricity are not common. We report here on a detailed study of supramolecular polymers formed in water by carboxylated naphtho-p-quinodimethane amphiphiles. We found that supramolecular polymerization of these amphiphiles in aqueous media yields crystalline assemblies with morphologies that included ribbons, helically rolled ribbons, and twisted filaments. This polymorphism was found to be controlled exclusively by repulsive electrostatic interactions controlled by the degree of protonation of the carboxylic head groups which also dictates the nature of supramolecular packing. Substoichiometric amounts of base lead to highly crystalline ribbons due to a decreased surface charge density and less electrostatic repulsion. Increasing deprotonation results in helically rolled ribbons with a different polymorph crystal lattice, whereas excessive deprotonation leads to twisted filaments with maximum surface charge density. Ribbons, helical rolled ribbons, and twisted filaments revealed an increasing red shift in their visible absorption maxima. These crystalline assemblies could be potential candidates for solar energy materials and photocatalytic systems.
AB - Supramolecular polymers can emulate some of the physical properties of covalent polymers but offer new opportunities given the possibility of designing monomers that will form highly ordered assemblies with defined shapes. Internally ordered supramolecular polymers formed through nucleation-elongation self-assembly are well-known but highly crystalline examples which exhibit important properties such as light harvesting, charge transport, and ferroelectricity are not common. We report here on a detailed study of supramolecular polymers formed in water by carboxylated naphtho-p-quinodimethane amphiphiles. We found that supramolecular polymerization of these amphiphiles in aqueous media yields crystalline assemblies with morphologies that included ribbons, helically rolled ribbons, and twisted filaments. This polymorphism was found to be controlled exclusively by repulsive electrostatic interactions controlled by the degree of protonation of the carboxylic head groups which also dictates the nature of supramolecular packing. Substoichiometric amounts of base lead to highly crystalline ribbons due to a decreased surface charge density and less electrostatic repulsion. Increasing deprotonation results in helically rolled ribbons with a different polymorph crystal lattice, whereas excessive deprotonation leads to twisted filaments with maximum surface charge density. Ribbons, helical rolled ribbons, and twisted filaments revealed an increasing red shift in their visible absorption maxima. These crystalline assemblies could be potential candidates for solar energy materials and photocatalytic systems.
UR - http://www.scopus.com/inward/record.url?scp=85100201538&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85100201538&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.0c04123
DO - 10.1021/acs.chemmater.0c04123
M3 - Article
AN - SCOPUS:85100201538
VL - 33
SP - 706
EP - 718
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 2
ER -