Abstract
Alloys are normally mixtures of metallic elements used to search for superior functional properties compared with their individual components. Although a quintessential approach to better materials in metallurgy, the concept of alloying has been expanded to other inorganic materials and covalent polymers. We report here on alloy formation of small organic molecules structured as amphiphilic chromophores in water. Using X-ray scattering, microscopy, and optical spectroscopy, we unambiguously demonstrate the formation of supramolecular alloys with changes in physical, photophysical, and mechanical properties. Additionally, we identify single-crystalline, two-dimensional supramolecular polymers containing multiple molecular species, analogous to intermetallic compounds. The mechanism of alloy formation suggests the possibility of controlled growth in these supramolecular assemblies to create emergent functional structures.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 170-180 |
| Number of pages | 11 |
| Journal | Chem |
| Volume | 9 |
| Issue number | 1 |
| DOIs | |
| State | Published - Jan 12 2023 |
Funding
This work was supported by the U.S. Department of Energy (DOE), Office of Science , Basic Energy Sciences , under award no. DE-SC0020884 . Use of the Advanced Photon Source (APS) was supported by the U.S. DOE , Office of Science , Basic Energy Sciences , under contract no. DE-AC02-06CH11357 . Solution X-ray experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility , was supported by the U.S. DOE, Office of Basic Energy Sciences , under contract no. DE-AC02-06CH11357. This work made use of the Integrated Molecular Structure Education and Research Center (IMSERC) MS and NMR facilities at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental ( SHyNE ) Resource ( NSF ECCS-2025633 ), International Institute for Nanotechnology (IIN), and Northwestern University . This work also made use of the BioCryo and Keck-II facilities of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource ( NSF ECCS-2025633 ), the IIN , and Northwestern’s MRSEC program ( NSF DMR-1720139 ). Additional experiments were performed in the Keck Biophysics Facility, a shared resource of the Robert H. Lurie Comprehensive Cancer Center of Northwestern University, supported in part by the NCI Cancer Center support grant # P30 CA060553 . We thank Boris Harutyunyan (Northwestern University) for his help in understanding the molecular packing within our supramolecular systems. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences, under award no. DE-SC0020884. Use of the Advanced Photon Source (APS) was supported by the U.S. DOE, Office of Science, Basic Energy Sciences, under contract no. DE-AC02-06CH11357. Solution X-ray experiments were performed at the DuPont-Northwestern-Dow Collaborative Access Team (DND-CAT) located at Sector 5 of the Advanced Photon Source (APS). DND-CAT is supported by Northwestern University, The Dow Chemical Company, and DuPont de Nemours, Inc. Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under contract no. DE-AC02-06CH11357. This work made use of the Integrated Molecular Structure Education and Research Center (IMSERC) MS and NMR facilities at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), International Institute for Nanotechnology (IIN), and Northwestern University. This work also made use of the BioCryo and Keck-II facilities of Northwestern University's NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern's MRSEC program (NSF DMR-1720139). Additional experiments were performed in the Keck Biophysics Facility, a shared resource of the Robert H. Lurie Comprehensive Cancer Center of Northwestern University, supported in part by the NCI Cancer Center support grant #P30 CA060553. We thank Boris Harutyunyan (Northwestern University) for his help in understanding the molecular packing within our supramolecular systems. Conceptualization, A.D. H.S. and S.I.S.; methodology, A.D. H.S. E.P.B. L.Ð. A.N. Y.Y. and X.M.; investigation, A.D. H.S. E.P.B. L.Ð. A.N. Y.Y. and X.M.; funding acquisition, L.C.P. and S.I.S.; project administration, L.C.P. and S.I.S.; supervision, L.C.P. and S.I.S.; writing – original draft, A.D. H.S. E.P.B. A.N. L.C.P. and S.I.S.; writing – review & editing, A.D. H.S. E.P.B. L.Ð. A.N. Y.Y. X.M. L.C.P. and S.I.S. The authors declare no competing interests.
Keywords
- SDG9: Industry innovation and infrastructure
- living supramolecular polymerization
- seeded growth
- supramolecular alloys
- supramolecular polymers
- two-dimensional crystals
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Environmental Chemistry
- General Chemical Engineering
- Biochemistry, medical
- Materials Chemistry