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A deep cavitand binds long-chain trans , trans - and trans , cis -bis-formamide isomers in water solution giving a pair of caviplexes in a ca. 6040 ratio. Both caviplexes display in/out guest exchange dynamics that are slow on the 1 H NMR chemical shift timescale, but fast on the EXSY timescale. We apply diffusion-ordered NMR spectroscopy (DOSY) to characterize the caviplexes. On the diffusion timescale, the guest in/out exchange processes feature intermediate dynamics allowing the assessment of their kinetic stabilities. We found that the