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Unlike conventional CT assemblies, these systems combine host\u2013guest chemistry with intermolecular donor\u2013acceptor interactions, enabling simultaneous regulation of molecular packing, electronic coupling, and excited\u2010state processes. The coexistence of cavity\u2010confined complexation and exo\u2010wall CT assembly, together with the dynamic nature of host\u2013guest interactions, provides unique opportunities for constructing stimuli\u2010responsive materials whose structures and functions can be continuously modulated by external inputs. In this Review, we discuss the fundamental principles underlying the design and construction of macrocycle\u2010based CT cocrystals and highlight how adaptive host\u2013guest recognition governs CT interactions and emergent solid\u2010state properties. Recent advances in vapochromic sensing, molecular separation, photothermal conversion, luminescence modulation, and multifunctional integrated systems are systematically summarized, with particular emphasis on competitive and cooperative structural regulation mechanisms. Finally, we outline current challenges and future directions toward programmable, multicomponent, and application\u2010oriented CT materials. By establishing connections between supramolecular structure, CT behavior, and functional output, this Review aims to provide a conceptual framework for the development of next\u2010generation adaptive molecular solids.<\/jats:p>","DOI":"10.1002\/anie.5451795","type":"journal-article","created":{"date-parts":[[2026,8,12]],"date-time":"2026-08-12T17:10:32Z","timestamp":1786554632000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Macrocycle\u2010Based Charge\u2010Transfer Cocrystals: From Host\u2013Guest Recognition to Multifunctional Solid\u2010State Materials"],"prefix":"10.1002","volume":"65","author":[{"given":"Gengxin","family":"Wu","sequence":"first","affiliation":[{"name":"Key Laboratory of Automobile Materials MOE Department of Materials Science School of Materials Science and Engineering Jilin University  Changchun P. R. 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