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This limitation has hindered the broader exploitation of this unique class of coordination compounds across various fields of transition metal chemistry. Through a systematic comparison and detail analysis of a series of Cu\n                    <jats:sup>I<\/jats:sup>\n                    catenane complexes, we show in this work that the size of the interlocked rings and exocyclic substituents are important structural parameters that regulate the exposure of the metal coordination sphere, which also influences the coordination geometry, electronic structures, spectroscopic, photophysical and electrochemical properties, as well as thermodynamic stability, ligand exchange kinetics, and chemical reactivity of the coordinated metal. Relationship between the structural features of the catenane and the extent of these effects is also revealed. These insights not only faciliate the rational design of a new type of switchable catenane catalyst wherein the interlocked structure is preserved, but also establish new principles for leveraging the unique effects of mechanical interlocking for diverse applications involving coordination complexes.\n                  <\/jats:p>","DOI":"10.1002\/anie.202514599","type":"journal-article","created":{"date-parts":[[2025,10,7]],"date-time":"2025-10-07T04:27:05Z","timestamp":1759811225000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["Structural Dependence of Catenand Effect: Thermodynamic and Kinetic Modulation of Catenane Coordination Properties via Ring\u2010size and Exocyclic Substituent Variation"],"prefix":"10.1002","volume":"64","author":[{"given":"Yulin","family":"Deng","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Hong Kong Pokfulam Road Hong Kong 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