Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters

Kathrin L. Kollmannsberger, None Poonam, Cristiana Cesari, Rachit Khare, Tim Kratky, Maxime Boniface, Ondřej Tomanec, Jan Michalička, Edoardo Mosconi, Alessio Gagliardi, Sebastian Günther, Waldemar Kaiser, Thomas Lunkenbein, Stefano Zacchini, Julien Warnan, Roland A. Fischer

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

Precisely designing metal nanoparticles (NPs) is the cornerstone for maximizing their efficiency in applications like catalysis or sensor technology. Metal-organic frameworks (MOFs) with their defined and tunable pore systems provide a confined space to host and stabilize small metal NPs. In this work, the MOF encapsulation of various atom-precise clusters following the bottle-around-ship approach is investigated, providing general insights into the scaffolding mechanism. Eleven carbonyl-stabilized Pt(M) (M = Co, Ni, Fe, and Sn) clusters are employed for the encapsulation in the zeolitic imidazolate framework (ZIF)-8. Infrared and UV/Vis spectroscopy, density functional theory, and ab initio molecular dynamics revealed structure-encapsulation relationship guidelines. Thereby, cluster polarization, size, and composition were found to condition the scaffolding behavior. Encaging of [NBnMe3]2[Co8Pt4C2(CO)24] (Co8Pt4) is thus achieved as the first MOF-encapsulated bimetallic carbonyl cluster, Co8Pt4@ZIF-8, and is fully characterized including X-ray absorption near edge and extended X-ray absorption spectroscopy. ZIF-8 confinement not only promotes property changes, like the T-dependent magnetism, but it also further allows heat-induced ligand-stripping without altering the cluster size, enabling the synthesis of naked, heterometallic, close to atom-precise clusters.

Original languageEnglish
Pages (from-to)5475-5486
Number of pages12
JournalChemistry of Materials
Volume35
Issue number14
DOIs
StatePublished - 25 Jul 2023

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