Multifunctional and Stimuli-responsive Coordination Cages

Multifunctional and Stimuli-responsive Coordination Cages G. H. Clever * Department of Chemistry and Chemical Biology, TU Dortmund University, Germany guido.clever@tu -dortmund.de Banana -shaped bis-monodentate ligands react with Pd(II) cations to coordination compounds with a broad range of topologies from small Pd 2L4 cages, their interpenetrated dimers, rings of various size up to large Pd 24L48 spheres. 1 We introduce stimuli-responsive behaviour triggered by small molecules or light leading to the modulation of guest affinity 2 or complete structural reorganization (Figure a). 3 Interpenetrated double cages consisting of donor and acceptor moieties were shown to undergo light-induced charge separation but suffer from a lack of control over stoichiometry and stereochemistry (Figure b). 4 Therefore, we recently started to apply principles of geometric shape complementarity to control the structure and composition of heteroleptic cages (Figure c). 5 On the other hand, circularly polarized luminescence (CPL) was observed for chiral Pt(II) complexes (Figure d). 6 Advanced self -assembly strategies will enable the targeted synthesis of supra-molecular systems and materials with increasing structural and functional complexity. Figure 1 Light -responsive coordination cages and chiral organometallic luminophors 1. Reviews: a) M. Han, D. M. Engelhard, G. H. Clever, Chem. Soc. Rev. 2014, 43, 1848; b) M. Frank, M. D. Johnstone, G. H. Clever, Chem. Eur. J. 2016 , 22 , 14104. Recent examples: c) W. M. Bloch, J. J. Holstein, B. Dittrich, W. Hiller, G. H. Clever, Angew. Chem. Int. Ed. 2018, 57, 5534; d) R. Zhu, I. Regeni, J. J. Holstein, B. Dittrich, M. Simon, S. Prévost, M. Gradzielski, G. H. Clever, Angew. Chem. Int. Ed. 2018 , DOI: 10.1002/ani e.201806047. 2. a) S. Löffler, J. Lübben, L. Krause, D. Stalke, B. Dittrich, G. H. Clever, J. Am. Chem. Soc. 2015, 137, 1060; b) M. Han, R. Michel, B. He, Y. -S. Chen, D. Stalke, M. John, G. H. Clever, Angew. Chem. Int. Ed. 2013 , 52 , 1319. 3. a) R. Zhu, J. Lübben, B. Dittrich, G. H. Clever, Angew. Chem. Int. Ed. 2015, 54, 2796; b) M. Han, Y. Luo, B. Damaschke, L. Gómez, X. Ribas, A. Jose, P. Peretzki, M. Seibt, G. H. Clever, Angew. Chem. Int. Ed. 2016, 55 , 445 . 4. M. Frank, J. Ahrens, I. Bejenke, M. Krick, D. Schwarzer, G. H. Clever, J. Am. Chem. Soc. 2016 , 138 , 8279. 5. a) W. M. Bloch, Y. Abe, J. J. Holstein, C. M. Wandtke, B. Dittrich, G. H. Clever, J. Am. Chem. Soc. 2016, 138, 13750; b) W. M. Bloch, J. J. Holstein, W. Hiller, G. H. Clever, Angew. Chem. Int. Ed. 2017 , 56 , 8285. 6. T. R. Schulte, J. J. Holstein, L. Krause, R. Michel, D. Stalke, E. Sakuda, K. Umakoshi, G. Longhi, S. Abbate, G. H. Clever, J. Am. Chem. Soc. 2017 , 139 , 6863.