Li, Ru-JinHan, MuxinTessarolo, JacopoHolstein, Julian J.Lübben, JensDittrich, BirgerVolkmann, ChristianFinze, MaikJenne, CarstenClever, Guido H.2019-06-132019-06-132019-03-21http://hdl.handle.net/2003/3809310.17877/DE290R-20075A new series of [Pd2(L)4] cages based on photochromic dithienylethene (DTE) ligands allowed us to gain insight into the successive photoswitching of multiple DTE moieties in a confined metallo‐supramolecular assembly. Three new X‐ray structures of [Pd2(o‐L4)4], [Pd2(o‐L1)2(c‐L1)2] and [Pd2(c‐L1)4] (o‐L and c‐L = open and closed forms of DTE ligands, respectively) were obtained. The structures deliver snapshots of three different combinations of DTE photoisomeric states within the cage, facilitating a comparison of the all‐open with the all‐closed, and most notably, an intermediate form where open and closed switches co‐exist in the same cage. Moreover, a series of spherical anionic borate clusters was introduced in order to study their roles in the light‐controllable host–guest chemistry. The binding guests show higher affinities with the flexible open cage [Pd2(o‐L1)4] than with the rigid closed cage [Pd2(c‐L1)4]. For the [B12F12]2− guest, thermodynamic data obtained from NMR experiments was compared to results from isothermal titration calorimetry (ITC).enhttps://creativecommons.org/licenses/by-nc/4.0/Coordination cagesDithienyletheneHost guest systemsPhotoswitchesSupramolecular chemistry540article (journal)