Steering the Ultrafast Opening and Closure Dynamics of a Photochromic Coordination Cage by Guest Molecules

Photochemical studies on supramolecular hosts that can encapsulate small guest molecules commonly focus on three aspects: photoswitching the cage to release or trap the guest, the effect of the confining environment on the guest, and light‐induced exciton or charge transfer within the cage structure. Here, we exploit ultrafast spectroscopy to address how the guest alters the photoswitching characteristics of the cage. For this, the impacts of three disparate guest compounds on ring‐opening or ring‐closure of a dithienylethene (DTE) ligand in a photoswitchable DTE‐based coordination cage are juxtaposed. The guest modulates both outcome and timescale of the cage's photodynamics, by an interplay of structural strain, heavy‐atom effect, and enhancement of charge‐transfer processes exercised by the guest on the photo‐excited cage. The approach might prove beneficial for attuning the applicability of photoswitchable nanocontainers and desired guest compounds.