ERC Consolidator Grant RAMSES

Reactivity and Assembly of Multifunctional, Stimuli-responsive Encapsulation Structures

https://cordis.europa.eu/project/id/683083/reporting

Objectives

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.

Further information

How to explain to your grandmother

Scientific Approach

ERC RAMSES Publications

Picture of a heteroleptic Pd2A2B2 cage showing a CPL effect

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

Animated gif showing phosphate binding in a Pd2L4 cage

"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.
(Hot Paper)

TOC figure showing a photoinduced host-to-guest electron transfer and the corresponding transient absorption spectra

"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.

Animated picture of the chirality transfer in a host-guest system showing a CPL effect

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)

TOC figure showing the biphasic polycondensation with a cage-like surfactant

"Nonaqueous Emulsion Polycondensation enabled by a Self-Assembled Cage-like Surfactant"
S. Ganta, C. Drechsler, Y.-T. Chen, G. H. Clever, Chem. Eur. J. 2022, 28, e202104228.

Abstract figure showing metal-oxide microcapsules and the TEM setup

"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.

Animated picture of palladium based cages showing different structures and C60 binding

"Cooperativity of steric bulk and H-bonding in coordination sphere engineering: heteroleptic Pd^II 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.

Animiertes Bild eines Wirt-Gast Komplexes außerhalb des thermodynamischen Gleichgewichts

"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)

TOC figure showing three heterobimetallic cubes with their spin-crossover behavior

"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.

"Integrative Assembly of Heteroleptic Tetrahedra Controlled by Backbone Steric Bulk"
J. Tessarolo, H. Lee, E. Sakuda, K. Umakoshi, G. H. Clever, J. Am. Chem. Soc. 2021, 143, 6339.

"Increasing Structural and Functional Complexity in Self-Assembled Coordination Cages"
S. Pullen, J. Tessarolo, G. H. Clever, Chem. Sci. 2021, 12, 7269-7293.

Quinoline-based cages with photoswitchable ligands

"Multi-Stimuli Control over Assembly and Guest Binding in Metallo- Supramolecular Hosts based on DTE Photoswitches"
R. Li, J. Tessarolo, H. Lee, G. H. Clever, J. Am. Chem. Soc. 2021, 143, 3865.

Palladium cage based on Michler´s ketone, methylene blue, rhodamine B and crystal violet.

"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)

See video feature on TU Dortmund Youtube Channel

Heteroleptic cages with backbone-bridged ligands

"Backbone-Bridging Promotes Diversity in Heteroleptic Cages"

K. Wu, B. Zhang, C. Drechsler, J. J. Holstein, G. H. Clever, Angew. Chem. Int. Ed. 2021, 60, 6403.

TOC picture showing a complex-to-complex transformation in a reaction flask

"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.

"A New Mechanically-Interlocked [Pd2L4] Cage Motif by Dimerization of two Peptide-based Lemniscates"

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)

Schematic representation of a ligand-modified oligonucleotide, that folds into a G-quadruplex structure giving rise to a heteroleptic chelate environment suitable for transition metal binding.

"Heteroleptic Coordination Environments in Metal-Mediated DNA G-Quadruplexes"

P. M. Punt, L. M. Stratmann, S. Sevim, L. Knauer, C. Strohmann, G. H. Clever, Front. Chem. 2020, 8, 26.

Schematic representation of the effect of steric hindrance around the coordination environment in bis-monodentate ligands leading to different coordination products acting as host structures for fullerene binding.

"Tunable Fullerene Affinity of Cages, Bowls and Rings Assembled by Pd(II) Coordination Sphere Engineering"

B. Chen, S. Horiuchi, J. J. Holstein, J. Tessarolo, G. H. Clever, Chem. Eur. J. 2019, 25, 14921.

Trapped ion mobility-derived mobilograms of a complex mixture of heteroleptic coordination cages shows clear differentiation of different species.

"Resolution of Minor Size Differences in a Family of Heteroleptic Coordination Cages by Trapped Ion Mobility ESI-MS"

K. E. Ebbert, L. Schneider, A. Platzek, C. Drechsler, B. Chen, R. Rudolf, G. H. Clever, Dalton Trans. 2019, 48, 11070.

Schematic representation of a bowl-shaped coordination compound that binds fullerene and acts as a supramolecular protecting group to control functionalization.

"Pd(II) Coordination Sphere Engineering: Pyridine Cages, Quinoline Bowls and Heteroleptic Pills Binding One or Two Fullerenes"

B. Chen, J. J. Holstein, S. Horiuchi, W. G. Hiller, G. H. Clever, J. Am. Chem. Soc. 2019, 141, 8907.

Schematic representation of successive photoswitching in photochromic DTE-based coordination cages.

"Successive Photoswitching and Derivatization Effects in Photochromic DTE-based Coordination Cages"

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.

Schematic representation of a chiral helicene-based bis-monodentate ligand that assembles upon palladium addition into an interpenetrated coordination cage.

"Chiral Self-Discrimination and Guest Recognition in Helicene-based Coordination Cages"

T. R. Schulte, J. J. Holstein, G. H. Clever, Angew. Chem. Int. Ed. 2019, 58, 5562.

Schematic representation, X-ray structures and CD spectra of a photochromic coordination cage interacting with a chiral guest.

"Mechanistic Interplay between Light-Switching and Guest-Binding in Photochromic [Pd₂Dithienylethene₄] Coordination Cages"

R. Li, J. J. Holstein, W. G. Hiller, J. Andréasson, G. H. Clever, J. Am. Chem. Soc. 2019, 141, 2097.

Schematic representation of the assembly of an amphiphilic coordination cage-based emulsifier and cryo-TEM images of hollow spherical vesicles formed in acetonitril.

"Rational Design of an Amphiphilic Coordination Cage-based Emulsifier"

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.

Schematic representation of multifunctional metal-organic frameworks and heteroleptic coordination cages.

"Mixed-Ligand Metal-Organic Frameworks and Heteroleptic Coordination Cages as Multifunctional Scaffolds – A Comparison"

S. Pullen, G. H. Clever, Acc. Chem. Res. 2018, 51, 3052.

Schematic representation of a rational design of heteroleptic coordination cages based on donor-site-engineering.

"Donor-site-directed Rational Assembly of Heteroleptic cis-[Pd₂L₂L'₂] Coordination Cages from Picolyl Ligands"

R. Zhu, W. M. Bloch, J. J. Holstein, S. Mandal, L. V. Schäfer, G. H. Clever, Chem. Eur. J. 2018, 24, 12976.

(Hot Paper)

X-ray structure and TEM image of an interlocked M8L16 container.

"Hierarchical Assembly of an Interlocked M₈L₁₆ Container"

W. M. Bloch, J. J. Holstein, B. Dittrich, W. Hiller, G. H. Clever, Angew. Chem. Int. Ed. 2018, 57, 5534.

"Integrative self-sorting of coordination cages based on 'naked' metal ions "

W. M. Bloch, G. H. Clever, Chem. Commun. 2017, 53, 8506.

"Morphological Control of Heteroleptic cis- and trans-Pd₂L₂L'₂ Cages"

W. M. Bloch, J. J. Holstein, W. Hiller, G. H. Clever, Angew. Chem. Int. Ed. 2017, 56, 8285.

"Geometric Complementarity in Assembly and Guest Recognition of a Bent Heteroleptic cis-[Pd₂L^A₂L^B₂] Coordination Cage"

W. M. Bloch, Y. Abe, J. J. Holstein, C. M. Wandtke, B. Dittrich, G. H. Clever, J. Am. Chem. Soc. 2016, 138, 13750.

"Light-induced Charge Separation in Densely Packed Donor-Acceptor Coordination Cages"

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.

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