Induced Fit and Mobility of Cycloalkanes within Nanometer-Sized Confinements at 5 K.

Autor: Ahsan A; Department of Physics, University of Basel, Klingelbergstrasse 82, 4056 Basel, Switzerland., Buimaga-Iarinca L; CETATEA, National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat, 400293 Cluj-Napoca, Romania., Nijs T; Department of Physics, University of Basel, Klingelbergstrasse 82, 4056 Basel, Switzerland., Nowakowska S; Department of Physics, University of Basel, Klingelbergstrasse 82, 4056 Basel, Switzerland., Sk R; Department of Physics, University of Basel, Klingelbergstrasse 82, 4056 Basel, Switzerland., Mousavi SF; Department of Physics, University of Basel, Klingelbergstrasse 82, 4056 Basel, Switzerland., Heydari M; Laboratory for X-ray Nanoscience and Technologies, Paul Scherrer Institut (PSI), 5232 Villigen, Switzerland., Stöhr M; Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands., Zaman SS; Integrated Sciences and Mathematics, Habib University, Block 18, Gulistan-e-Jauhar, University Avenue, Off Shahrah-e-Faisal Road, Karachi 75290, Sindh, Pakistan., Morari C; CETATEA, National Institute for Research and Development of Isotopic and Molecular Technologies, 67-103 Donat, 400293 Cluj-Napoca, Romania., Gade LH; Anorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany., Jung TA; Laboratory for X-ray Nanoscience and Technologies, Paul Scherrer Institut (PSI), 5232 Villigen, Switzerland.
Jazyk: angličtina
Zdroj: The journal of physical chemistry letters [J Phys Chem Lett] 2022 Aug 18; Vol. 13 (32), pp. 7504-7513. Date of Electronic Publication: 2022 Aug 09.
DOI: 10.1021/acs.jpclett.2c01592
Abstrakt: Host-guest architectures provide ideal systems for investigating site-specific physical and chemical effects. Condensation events in nanometer-sized confinements are particularly interesting for the investigation of intermolecular and molecule-surface interactions. They may be accompanied by conformational adjustments representing induced fit packing patterns. Here, we report that the symmetry of small clusters formed upon condensation, their registry with the substrate, their lateral packing, and their adsorption height are characteristically modified by the packing of cycloalkanes in confinements. While cyclopentane and cycloheptane display cooperativity upon filling of the hosting pores, cyclooctane and to a lesser degree cyclohexane diffusively redistribute to more favored adsorption sites. The dynamic behavior of cyclooctane is surprising at 5 K given the cycloalkane melting point of >0 °C. The site-specific modification of the interaction and behavior of adsorbates in confinements plays a crucial role in many applications of three-dimensional porous materials as gas storage agents or catalysts/biocatalysts.
Databáze: MEDLINE
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