Zitieren Sie bitte immer diesen URN: urn:nbn:de:kobv:b43-589117
Effects of Ligand Substituents on the Character of Zn-Coordination in Zeolitic Imidazolate Frameworks
- Due to their favorable properties and high porosity, zeolitic imidazolate frameworks (ZIFs) have recently received much limelight for key technologies such as energy storage, optoelectronics, sensorics, and catalysis. Despite widespread interest in these materials, fundamental questions regarding the zinc coordination environment remain poorly understood. By focusing on zinc(II)2-methylimidazolate (ZIF-8) and its tetrahedrally coordinated analogues with Br-, Cl-, and H-substitution in the 2-ring position, we aim to clarify how variations in the local environment of Zn impact the charge distribution and the electronic properties of these materials. Our results from densityfunctional theory confirm the presence of a Zn coordinative bond with a large polarization that is quantitatively affected by different substituents on the organic ligand. Moreover, our findings suggest that the variations in the Zn coordination induced by the functionalization have a negligible effect on theDue to their favorable properties and high porosity, zeolitic imidazolate frameworks (ZIFs) have recently received much limelight for key technologies such as energy storage, optoelectronics, sensorics, and catalysis. Despite widespread interest in these materials, fundamental questions regarding the zinc coordination environment remain poorly understood. By focusing on zinc(II)2-methylimidazolate (ZIF-8) and its tetrahedrally coordinated analogues with Br-, Cl-, and H-substitution in the 2-ring position, we aim to clarify how variations in the local environment of Zn impact the charge distribution and the electronic properties of these materials. Our results from densityfunctional theory confirm the presence of a Zn coordinative bond with a large polarization that is quantitatively affected by different substituents on the organic ligand. Moreover, our findings suggest that the variations in the Zn coordination induced by the functionalization have a negligible effect on the electronic structure of the considered compounds. On the other hand, halogen terminations of the ligands lead to distinct electronic contributions in the vicinity of the frontier region which ultimately reduce the band gap size by a few hundred millielectron volts. Experimental results obtained from X-ray absorption spectroscopy (Zn K-edge) confirm the trends predicted by theory and, together with them, contribute to a better understanding of the structure−property relationships that are needed to tailor ZIFs for target applications.…
Autor*innen: | Joshua Edzards, Holger-Dietrich SaßnickORCiD, Ana Guilherme BuzanichORCiD, Ana M. ValenciaORCiD, Franziska EmmerlingORCiD, Sebastian BeyerORCiD, Caterina CocchiORCiD |
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Dokumenttyp: | Zeitschriftenartikel |
Veröffentlichungsform: | Verlagsliteratur |
Sprache: | Englisch |
Titel des übergeordneten Werkes (Englisch): | The Journal of Physical Chemistry C |
Jahr der Erstveröffentlichung: | 2023 |
Organisationseinheit der BAM: | 6 Materialchemie |
6 Materialchemie / 6.3 Strukturanalytik | |
Veröffentlichende Institution: | Bundesanstalt für Materialforschung und -prüfung (BAM) |
Verlag: | American Chemical Society (ACS) |
Jahrgang/Band: | 127 |
Ausgabe/Heft: | 43 |
Erste Seite: | 21456 |
Letzte Seite: | 21464 |
DDC-Klassifikation: | Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten |
Freie Schlagwörter: | Coatings and Films; Electronic; General Energy; Optical and Magnetic Materials; Physical and Theoretical Chemistry; Surfaces |
Themenfelder/Aktivitätsfelder der BAM: | Material |
DOI: | 10.1021/acs.jpcc.3c06054 |
URN: | urn:nbn:de:kobv:b43-589117 |
ISSN: | 1932-7447 |
Verfügbarkeit des Dokuments: | Datei für die Öffentlichkeit verfügbar ("Open Access") |
Lizenz (Deutsch): | Creative Commons - CC BY - Namensnennung 4.0 International |
Datum der Freischaltung: | 27.11.2023 |
Referierte Publikation: | Ja |
Datum der Eintragung als referierte Publikation: | 27.11.2023 |
Schriftenreihen ohne Nummerierung: | Wissenschaftliche Artikel der BAM |