Bäumer, Nils ; Kartha, Kalathil K. ; Palakkal, Jasnamol P. ; Fernández, Gustavo (2020)
Morphology control in metallosupramolecular assemblies through solvent-induced steric demand.
In: Soft Matter, 16 (29)
doi: 10.1039/D0SM00537A
Artikel, Bibliographie
Kurzbeschreibung (Abstract)
Controlling the supramolecular self-assembly of pi-conjugated systems into defined morphologies is a prerequisite for the preparation of functional materials. In recent years, the development of sophisticated sample preparation protocols and modulation of various experimental conditions (solvent, concentration, temperature,etc.) have enabled precise control over aggregation pathways of different types of monomer units. A common method to achieve pathway control consists in the combination of two miscible solvents in defined proportions - a "poor" and "good" solvent. However, the role of solvents of opposed polarity in the self-assembly of a given building block still remains an open question. Herein, we unravel the effect of aggregation-inducing solvent systems of opposed polarity (aqueousvs.non-polar media) on the supramolecular assembly of a new bolaamphiphilic Pt(ii) complex. A number of experimental methods show a comparable molecular packing in both media driven by a synergy of solvophobic, aromatic and weak hydrogen-bonding interactions. However, morphological analysis of the respective aggregates in aqueous and non-polar media reveals a restricted aggregate growth in aqueous media into spherical nanoparticles and a non-restricted 2D-nanosheet formation in non-polar media. These findings are attributed to a considerably more efficient solvation and, in turn, increased steric demand of the hydrophilic chains in aqueous media than in nonpolar media, which can be explained by the entrapment of water molecules in the hydrophilic aggregate shellviahydrogen bonds. Our findings reveal that the different solvation of peripheral solubilizing groups in solvents of opposed polarity is an efficient method for morphology control in self-assembly.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2020 |
| Autor(en): | Bäumer, Nils ; Kartha, Kalathil K. ; Palakkal, Jasnamol P. ; Fernández, Gustavo |
| Art des Eintrags: | Bibliographie |
| Titel: | Morphology control in metallosupramolecular assemblies through solvent-induced steric demand |
| Sprache: | Englisch |
| Publikationsjahr: | 7 August 2020 |
| Verlag: | Royal Society of Chemistry |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Soft Matter |
| Jahrgang/Volume einer Zeitschrift: | 16 |
| (Heft-)Nummer: | 29 |
| DOI: | 10.1039/D0SM00537A |
| Kurzbeschreibung (Abstract): | Controlling the supramolecular self-assembly of pi-conjugated systems into defined morphologies is a prerequisite for the preparation of functional materials. In recent years, the development of sophisticated sample preparation protocols and modulation of various experimental conditions (solvent, concentration, temperature,etc.) have enabled precise control over aggregation pathways of different types of monomer units. A common method to achieve pathway control consists in the combination of two miscible solvents in defined proportions - a "poor" and "good" solvent. However, the role of solvents of opposed polarity in the self-assembly of a given building block still remains an open question. Herein, we unravel the effect of aggregation-inducing solvent systems of opposed polarity (aqueousvs.non-polar media) on the supramolecular assembly of a new bolaamphiphilic Pt(ii) complex. A number of experimental methods show a comparable molecular packing in both media driven by a synergy of solvophobic, aromatic and weak hydrogen-bonding interactions. However, morphological analysis of the respective aggregates in aqueous and non-polar media reveals a restricted aggregate growth in aqueous media into spherical nanoparticles and a non-restricted 2D-nanosheet formation in non-polar media. These findings are attributed to a considerably more efficient solvation and, in turn, increased steric demand of the hydrophilic chains in aqueous media than in nonpolar media, which can be explained by the entrapment of water molecules in the hydrophilic aggregate shellviahydrogen bonds. Our findings reveal that the different solvation of peripheral solubilizing groups in solvents of opposed polarity is an efficient method for morphology control in self-assembly. |
| Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Dünne Schichten |
| Hinterlegungsdatum: | 20 Nov 2020 09:08 |
| Letzte Änderung: | 20 Nov 2020 09:08 |
| PPN: | |
| Projekte: | We acknowledge the European Commission (ERC-StG-2016 SUPRACOP-715923) for funding. |
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