Systems chemistry: new external stimuli, molecular tools and applications

• Applicant: Professor Dr. Max von Delius
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2014 to 2022
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 239129828

• Final Report Year: 2023

Final Report Abstract

The aim of the project entitled "Systems Chemistry: New External Stimuli, Molecular Tools and Applications" was to give impetus to the research field of "Systems Chemistry", which was still entirely new in 2014. In retrospect, we achieved this aim at all relevant levels. For instance, we were able to establish four new molecular tools for systems chemistry and supramolecular chemistry (orthoester exchange, trithioorthoester exchange, amidinium exchange and trialkoxysilane exchange). With the manipulation of dynamic disulfide systems by ultrasound, we were also able to achieve our goal of establishing a new external stimulus that is of high importance for the field. These research advances are relevant for biomedicine (drug delivery) and for materials science (smart and degradable molecules and polymers). We were able to show, for example, that orthoester cages are suitable for transporting ions through biological membranes (patent published) and can be decomposed in a pH-dependent manner. Likewise, we were able to show that orthoester chemistry is suitable for the production of polymers that are largely similar to well-known polyethylene (PE) plastics, but are much more easily degradable when exposed to water and acid. Our fundamental work on the effect of ultrasound on disulfides has been taken up by multiple research groups dedicated to drug transport and ultrasound-induced release.

Publications

• Augmented Reality App SuprAR (for use in lecture “Supramolecular Chemistry”)
  
  
• Novel crown ether complexes and methods for producing the same European
  M. von Delius, R. Brachvogel
  
• “Rezeptoren im Verbund” Nachrichten aus der Chemie, 62, 522-525
  M. von Delius
  (See online at https://doi.org/10.1002/nadc.201490158)
• Increased short circuit current in an azafullerene-based organic solar cell Chemical Communications, 51, 1128-1130
  W. Cambarau, U. F. Fritze, A. Viterisi, E. Palomares, M. von Delius
  (See online at https://doi.org/10.1039/C4CC08094G)
• NMR Studies on Li+, Na+ and K+ Complexes of Orthoester Cryptand o-Me2-1.1.1 International Journal of Molecular Sciences, 16, 20641-20656
  R. Brachvogel, H. Maid, M. von Delius
  (See online at https://doi.org/10.3390/ijms160920641)
• Orthoester exchange: a tripodal tool for dynamic covalent and systems chemistry Chemical Science, 6, 1399-1403
  R. Brachvogel, M. von Delius
  (See online at https://doi.org/10.1039/C4SC03528C)
• Self-assembly of dynamic orthoester cryptates Nature Communications, 6, 7129
  R. Brachvogel, F. Hampel, M. von Delius
  (See online at https://doi.org/10.1038/ncomms8129)
• Dynamic disulfide metathesis induced by ultrasound Chemical Communications, 52, 6363-6366
  U. F. Fritze, M. von Delius
  (See online at https://doi.org/10.1039/C6CC02034H)
• Morphological and electrical control of fullerene dimerization determines organic photovoltaic stability Energy & Environmental Science, 9, 247-256.
  T. Heumüller, W. R. Mateker, A. Distler, U. F. Fritze, R. Cheachareon, W. Nguyen, M. Biele, M. Salvador, M. von Delius, H. Egelhaaf, M. D. McGehee, C. J. Brabec
  (See online at https://doi.org/10.1039/C5EE02912K)
• Optimized Syntheses of Optically Pure P-Alkene Ligands: Crystal Structures of a Pair of P-Stereogenic Diastereomers Synthesis, 48, 1117-1121
  A. Herrera, A. Linden, F. W. Heinemann, R. Brachvogel, M. von Delius, R. Dorta
  (See online at https://doi.org/10.1055/s-0035-1560410)
• Small Is (also) Beautiful: Dynamic Covalent Self-Assembly of Cryptates Synlett, 27, 177-180.
  M. von Delius
  (See online at https://doi.org/10.1055/s-0035-1560221)
• The Dynamic Covalent Chemistry of Esters, Acetals and Orthoesters European Journal of Organic Chemistry, 3662-3670
  R. Brachvogel, M. von Delius
  (See online at https://doi.org/10.1002/ejoc.201600388)
• Adaptive Behaviour of Dynamic Orthoester Cryptands Angewandte Chemie International Edition, 56, 776-781
  O. Shyshov, R. Brachvogel, T. Bachmann, R. Srikantharajah, D. Segets, F. Hampel, R. Puchta, M. von Delius
  (See online at https://doi.org/10.1002/anie.201609855)
• “Heterofullerenes: Doped Buckyballs” in: Chemical Synthesis and Applications of Graphene and Carbon Materials; Wiley-VCH, Weinheim, 191-216
  M. von Delius, A. Hirsch
  (See online at https://doi.org/10.1002/9783527648160.ch9)
• Disulfide-centered poly(methyl acrylates): four different stimuli to cleave a polymer Journal of Polymer Science Part A: Polymer Chemistry, 56, 1404-1411.
  U. F. Fritze, S. L. Craig, M. von Delius
  (See online at https://doi.org/10.1002/pola.29021)
• Evidence for anion-binding of all-cis hexafluorocyclohexane in solution and solid state Chemical Communications, 54, 4353-4355.
  O. Shyshov, K. A. Siewerth, M. von Delius
  (See online at https://doi.org/10.1039/C8CC01797B)
• Self-Assembled Orthoester Cryptands: Orthoester Scope, Post-Functionalization, Kinetic Locking and Tunable Degradation Kinetics Chemical Science, 9, 4785-4793
  H. Löw, E. Mena-Osteritz, M. von Delius
  (See online at https://doi.org/10.1039/C8SC01750F)
• Ammonium Complexes of Orthoester Cryptands are Inherently Dynamic and Adaptive Journal of the American Chemical Society, 141, 8868−8876
  X. Wang, O. Shyshov, M. Hanževački, C. Jäger, M. von Delius
  (See online at https://doi.org/10.1021/jacs.9b01350)
• Long-Chain Polyorthoesters as Degradable Polyethylene Mimics Macromolecules, 52, 2411−2420
  T. Haider, O. Shyshov, O. Suraeva, I. Lieberwirth, M. von Delius, F. R. Wurm
  (See online at https://doi.org/10.1021/acs.macromol.9b00180)
• Self-templated synthesis of an orthoformate in,in-cryptand and its bridgehead inversion by dynamic covalent exchange Chemical Communications, 55, 11434-11437
  H. Löw, E. Mena-Osteritz, M. von Delius
  (See online at https://doi.org/10.1039/c9cc05968g)
• Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry Synlett, 30, 1988-1994.
  M. Bothe, G. Orrillo, R. Furlan, M. von Delius
  (See online at https://doi.org/10.1055/s-0039-1690992)
• „Über den Trend vom Molekül zum System“ Nachrichten aus der Chemie, 67, 62-65
  M. von Delius, S. Hollstein
  (See online at https://doi.org/10.1002/nadc.20194087037)
• Self-Assembly, Adaptive Response and in,out-Stereoisomerism of Large Orthoformate Cryptands ChemPlusChem, 85, 108-112.
  H. Löw, E. Mena-Osteritz, K. M. Mullen, C. M. Jäger, M. von Delius
  (See online at https://doi.org/10.1002/cplu.202000254)
• Self-assembly of stimuli-responsive [2]rotaxanes by amidinium exchange Journal of the American Chemical Society, 143, 16448–16457
  O. Borodin, Y. Shchukin, C. C. Robertson, S. Richter, M. von Delius
  (See online at https://doi.org/10.1021/jacs.1c05230)
• Supramolecular Approaches for Taming the Chemo- and Regiochemistry of C60 Addition Reactions Organic Materials, 3, 146-154.
  S. B. Beil, M. von Delius
  (See online at https://doi.org/10.1055/s-0041-1727182)
• Anion-assisted amidinium exchange and metathesis Chemical Communications, 58, 10178 – 10181.
  O. Borodin, Y. Shchukin, J. Schmid, M. von Delius
  (See online at https://doi.org/10.1039/D2CC03425E)
• Dynamic Covalent Self-Assembly of Chloride- and Ion-Pair-Templated Cryptates Angewandte Chemie International Edition, e202201831
  S. Hollstein, O. Shyshov, M. Hanževački, J. Zhao, T. Rudolf, C. M. Jäger, M. von Delius
  (See online at https://doi.org/10.1002/anie.202201831)