TY - JOUR
T1 - Mechanistic Insights into ZIF-8 Encapsulation of Atom-Precise Pt(M) Carbonyl Clusters
AU - Kollmannsberger, Kathrin L.
AU - Poonam, None
AU - Cesari, Cristiana
AU - Khare, Rachit
AU - Kratky, Tim
AU - Boniface, Maxime
AU - Tomanec, Ondřej
AU - Michalička, Jan
AU - Mosconi, Edoardo
AU - Gagliardi, Alessio
AU - Günther, Sebastian
AU - Kaiser, Waldemar
AU - Lunkenbein, Thomas
AU - Zacchini, Stefano
AU - Warnan, Julien
AU - Fischer, Roland A.
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/7/25
Y1 - 2023/7/25
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85165653403&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.3c00807
DO - 10.1021/acs.chemmater.3c00807
M3 - Article
AN - SCOPUS:85165653403
SN - 0897-4756
VL - 35
SP - 5475
EP - 5486
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 14
ER -