In biochemical systems, combinations of specialized molecular entities are precisely arranged in space to give highly complex architectures. Sophisticated functionality, such as the selective chemical transformation of substrates inside enzymes, emerges from the interplay of the individual components that are often grouped around a nanoscopic cavity. Furthermore, control mechanisms based on the cooperative binding of signal substances may regulate the enzyme’s action.
Since the advent of supramolecular chemistry, scientists construct artificial systems with ever increasing complexity and functionality that promise to serve as the basis for future developments in bottom-up nanotechnology with applications in medicine (e.g. targeted drug delivery), smart diagnostics, catalysis, material science, molecular photonics, electronics and data processing.
Metal-mediated self-assembly is a mature technique to construct such discrete, nanosized objects. So far, however, the implementation of one type of organic ligand at a time is dominating the reported, highly symmetric structures, while the tailored integration of a set of different ligands requires sophisticated approaches to avoid narcissistic separation or formation of statistical libraries.
Nature demonstrates that the key to the most sophisticated systems lies in multi-functionalized structures. To achieve this level of complexity with artificial systems, we develop multiple strategies for the synthesis of heteroleptic coordination architectures. As a result, different functional elements can be precisely arranged inside or outside the cavity and their interplay will be studied. Combined with our recent achievements in host-guest switching, we aim at adjustable receptors, controllable molecular reaction chambers and multifunctional photo/redox systems.
Modular Enhancement of Circularly Polarized Luminescence in Pd2A2B2 heteroleptic cages
J. Tessarolo, E. Benchimol, A. Jouaiti, M. Wais Hosseini, G. H. Clever, Chem. Commun. 2023, DOI: 10.1039/D3CC00262D
"Endohedrally Functionalized Heteroleptic Coordination Cages for Phosphate Ester Binding"
A. Platzek, S. Juber, C. Yurtseven, S. Hasegawa, L. Schneider, C. Drechsler, K. E. Ebbert, R. Rudolf, Q.-Q. Yan, J. J. Holstein, L. V. Schäfer, G. H. Clever, Angew. Chem. Int. Ed. 2022, DOI: 10.1002/anie.202209305.
"Photoinduced Host-to-Guest Electron Transfer in a Self-Assembled Coordination Cage"
S. Ganta, J.-H. Borter, C. Drechsler, J. J. Holstein, D. Schwarzer, G. H. Clever, Org. Chem. Front. 2022, 9, 5485-5493.
Guest-modulated Circularly Polarized Luminescence by Ligand-to-Ligand Chirality Transfer in Heteroleptic Pd(II) Coordination Cages
K. Wu, J. Tessarolo, A. Baksi, G. H. Clever, Angew. Chem. Int. Ed. 2022, DOI: 10.1002/anie.202205725.
(Hot Paper, Front Cover)
"Coordination cage-based emulsifiers: templated formation of metal oxide microcapsules monitored by in situ LC-TEM"
S. Saha, Y.-T. Chen, S. Ganta, M. Gilles, B. Holzapfel, P. Lill, H. Rehage, C. Gatsogiannis, G. H. Clever, Chem. Eur. J. 2021, accepted.
"Cooperativity of steric bulk and H-bonding in coordination sphere engineering: heteroleptic PdII cages and bowls by design"
B. Chen, J. J. Holstein, A. Platzek, L. Schneider, K. Wu, G. H. Clever, Chem. Sci. 2022, 13, 1829 - 1834.
"Light-powered Dissipative Assembly of Diazocine Coordination Cages"
H. Lee, J. Tessarolo, D. Langbehn, A. Baksi, R. Herges, G. H. Clever, J. Am. Chem. Soc. 2022, 144, DOI: 10.1021/jacs.1c12011.
Official faculty news announcement with more information (German only)
"A Family of Heterobimetallic Cubes Shows Spin-Crossover Behaviour Near Room Temperature"
M. Hardy, J. Tessarolo, J. J. Holstein, N. Struch, N. Wagner, R. Weisbarth, M. Engeser, J. Beck, S. Horiuchi, G. H. Clever, A. Lützen, Angew. Chem. Int. Ed. 2021, 60, 22562-22569.
"Coal-Tar Dye-based Coordination Cages and Helicates"
I. Regeni, B. Chen, M. Frank, A. Baksi, J. J. Holstein, G. H. Clever, Angew. Chem. Int. Ed. 2021, 60, 5673.
(Highlighted in a press release by the Cluster of Excellence RESOLV)
"Dynamic Complex-to-Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions"
M. Hardy, N. Struch, J. J. Holstein, G. Schnakenburg, N. Wagner, M. Engeser, J. Beck, G. H. Clever, A. Lützen, Angew. Chem. Int. Ed. 2020, 59, 3195.
T. R. Schulte, J. J. Holstein, L. Schneider, A. Adam, G. Haberhauer, G. H. Clever, Angew. Chem. Int. Ed. 2020, 59, 22489.
(Hot Paper, Inside Cover)
(In collaboration with Prof. Gebhard Haberhauer from Duisburg-Essen University)
B. Chen, S. Horiuchi, J. J. Holstein, J. Tessarolo, G. H. Clever, Chem. Eur. J. 2019, 25, 14921.
K. E. Ebbert, L. Schneider, A. Platzek, C. Drechsler, B. Chen, R. Rudolf, G. H. Clever, Dalton Trans. 2019, 48, 11070.
B. Chen, J. J. Holstein, S. Horiuchi, W. G. Hiller, G. H. Clever, J. Am. Chem. Soc. 2019, 141, 8907.
R. Li, M. Han, J. Tessarolo, J. J. Holstein, J. Lübben, B. Dittrich, C. Volkmann, M. Finze, C. Jenne, G. H. Clever, ChemPhotoChem 2019, 3, 378.
R. Li, J. J. Holstein, W. G. Hiller, J. Andréasson, G. H. Clever, J. Am. Chem. Soc. 2019, 141, 2097.
S. Saha, B. Holzapfel, Y.-T. Chen, K. Terlinden, P. Lill, C. Gatsogiannis, H. Rehage, G. H. Clever, J. Am. Chem. Soc. 2018, 140, 17384.
R. Zhu, W. M. Bloch, J. J. Holstein, S. Mandal, L. V. Schäfer, G. H. Clever, Chem. Eur. J. 2018, 24, 12976.
W. M. Bloch, Y. Abe, J. J. Holstein, C. M. Wandtke, B. Dittrich, G. H. Clever, J. Am. Chem. Soc. 2016, 138, 13750.
M. Frank, J. Ahrens, I. Bejenke, M. Krick, D. Schwarzer, G. H. Clever, J. Am. Chem. Soc. 2016, 138, 8279.
Congratulations to Jennifer Ahrens (PhD student of collaboration partner Prof. Dirk Schwarzer, MPI for Biophysical Chemistry, Göttingen) for receiving a Poster Prize on the Bunsentagung 2016 for her contribution to our joint work. In addition, our work was featured on the cover of issue 5/2016 of the Bunsen Magazin.