Behavior of Constitutional Dynamic Networks: Competition, Selection, Self‐sorting in Cryptate Systems

Understandingdynamicsystemsis a crucialsteptowardthedesignof complexmatter.Here,we aim to studythe behaviorof ConstitutionalDynamicNetworks(CDNs)in conditionsofdynamiccompetition,takingcryptandsandmetalcationsas atestbed.TheCDNsof cryptateswereanalyzedby NMRspectroscopy.The experimentalresultswerecomplementedbyextensivenumericalsimulations,basedon a largeamountofthermodynamicandkineticdataavailablein the literatureforcryptates.Althoughthe CDN’soutputis a resultof the interplaybetweenthe individualstabilityconstantsof the complexesin amixture,the overalleffectmaybe governedby onlyone– themostthermodynamicallystablememberof a network.Signifi-cantly,thesefindingsindicatethatan increasein complexity(multiplicityand connectivity)of a systemmay,in conditionsofdynamiccompetition,resultin “simplexity”,i.e. a simplificationof the outputof the system.