Multi-stimuli Control over Assembly and Guest Binding in Metallo-supramolecular Hosts Based on Dithienylethene Photoswitches

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Mar 6

PMID 33673736

Citations 28

Authors

Ru-Jin Li

Jacopo Tessarolo

Haeri Lee

Guido H Clever

Affiliations

Soon will be listed here.

Abstract

It is difficult to assemble multi-component metallo-supramolecular architectures in a non-statistical fashion, which limits their development toward functional materials. Herein, we report a system of interconverting bowls and cages that are able to respond to various selective stimuli (light, ligands, anions), based on the self-assembly of a photochromic dithienylethene (DTE) ligand, , with Pd cations. By combining the concept of "coordination sphere engineering", relying on bulky quinoline donors, with reversible photoswitching between the ligand's open (-) and closed (-) forms, a [Pd(-)] cage (-) and a [Pd(-)] bowl (-) were obtained, respectively. This structural rearrangement modulates the system's guest uptake capabilities. Among three bis-sulfonate guests (, , and ), the cage can encapsulate only the smallest (), while the bowl binds all of them. Bowl - was further used to synthesize a series of heteroleptic cages, [PdLL], representing a motif never reported before. Additional ligands (), with short or long arms, tune the cavity size, thus enabling or preventing guest uptake. Addition of Br/Ag makes it possible to change the overall charge, again triggering guest uptake and release, as well as fourth ligand de-/recomplexation. In combination, site-selective introduction of functionality and application of external stimuli lead to an intricate system of hosts with different guest preferences. A high degree of complexity is achieved through cooperativity between only a few components.

Citing Articles

Solvent-Controlled Separation of Integratively Self-Sorted PdL L Coordination Cages.

Ebbert K, Sendzik F, Neukirch L, Eberlein L, Platzek A, Kibies P Angew Chem Int Ed Engl. 2024; 64(4):e202416076.

PMID: 39377194 PMC: 11753612. DOI: 10.1002/anie.202416076.

Synthesis, Characterization, and Photochemistry of a GaL Coordination Cage with Dithienylethene-Catecholate Ligands.

Carbonell A, Izquierdo I, Guzman Rios D, Norjmaa G, Ujaque G, Martinez-Martinez A Inorg Chem. 2024; 63(42):19872-19884.

PMID: 39375865 PMC: 11497204. DOI: 10.1021/acs.inorgchem.4c03279.

Photoswitchable Catalysis by a Self-Assembled Molecular Cage.

DiNardi R, Rasheed S, Capomolla S, Chak M, Middleton I, Macreadie L J Am Chem Soc. 2024; 146(31):21196-21202.

PMID: 39051845 PMC: 11311219. DOI: 10.1021/jacs.4c04846.

Photoswitching of Co(ii)-based coordination cages containing azobenzene backbones.

Tipping M, Prunonosa Lara L, Solea A, von Krbek L, Ward M Chem Sci. 2024; 15(22):8488-8499.

PMID: 38846406 PMC: 11151815. DOI: 10.1039/d4sc01575d.

A water-soluble Pd molecular tweezer for selective encapsulation of isomeric quinones and their recyclable extraction.

Prajapati D, Bhandari P, Zangrando E, Mukherjee P Chem Sci. 2024; 15(10):3616-3624.

PMID: 38455025 PMC: 10915840. DOI: 10.1039/d3sc05093a.

References

Chen B, Horiuchi S, Holstein J, Tessarolo J, Clever G . Tunable Fullerene Affinity of Cages, Bowls and Rings Assembled by Pd Coordination Sphere Engineering. Chemistry. 2019; 25(65):14921-14927. PMC: 6899814. DOI: 10.1002/chem.201903317. View

Tam A, Yam V . Recent advances in metallogels. Chem Soc Rev. 2013; 42(4):1540-67. DOI: 10.1039/c2cs35354g. View

Hammerich M, Schutt C, Stahler C, Lentes P, Rohricht F, Hoppner R . Heterodiazocines: Synthesis and Photochromic Properties, Trans to Cis Switching within the Bio-optical Window. J Am Chem Soc. 2016; 138(40):13111-13114. DOI: 10.1021/jacs.6b05846. View

Sun Y, Chen C, Stang P . Soft Materials with Diverse Suprastructures via the Self-Assembly of Metal-Organic Complexes. Acc Chem Res. 2019; 52(3):802-817. PMC: 6497072. DOI: 10.1021/acs.accounts.8b00663. View

Sun Q, Iwasa J, Ogawa D, Ishido Y, Sato S, Ozeki T . Self-assembled M24L48 polyhedra and their sharp structural switch upon subtle ligand variation. Science. 2010; 328(5982):1144-7. DOI: 10.1126/science.1188605. View

Xu L, Zhang D, Ronson T, Nitschke J . Improved Acid Resistance of a Metal-Organic Cage Enables Cargo Release and Exchange between Hosts. Angew Chem Int Ed Engl. 2020; 59(19):7435-7438. PMC: 7217015. DOI: 10.1002/anie.202001059. View

Bloch W, Abe Y, Holstein J, Wandtke C, Dittrich B, Clever G . Geometric Complementarity in Assembly and Guest Recognition of a Bent Heteroleptic cis-[PdLL] Coordination Cage. J Am Chem Soc. 2016; 138(41):13750-13755. DOI: 10.1021/jacs.6b08694. View

Yoshizawa M, Klosterman J, Fujita M . Functional molecular flasks: new properties and reactions within discrete, self-assembled hosts. Angew Chem Int Ed Engl. 2009; 48(19):3418-38. DOI: 10.1002/anie.200805340. View

Saha S, Holzapfel B, Chen Y, Terlinden K, Lill P, Gatsogiannis C . Rational Design of an Amphiphilic Coordination Cage-Based Emulsifier. J Am Chem Soc. 2018; 140(50):17384-17388. DOI: 10.1021/jacs.8b10991. View

10.

Cook T, Zheng Y, Stang P . Metal-organic frameworks and self-assembled supramolecular coordination complexes: comparing and contrasting the design, synthesis, and functionality of metal-organic materials. Chem Rev. 2012; 113(1):734-77. PMC: 3764682. DOI: 10.1021/cr3002824. View

11.

Cook T, Stang P . Recent Developments in the Preparation and Chemistry of Metallacycles and Metallacages via Coordination. Chem Rev. 2015; 115(15):7001-45. DOI: 10.1021/cr5005666. View

12.

Zarra S, Wood D, Roberts D, Nitschke J . Molecular containers in complex chemical systems. Chem Soc Rev. 2014; 44(2):419-32. DOI: 10.1039/c4cs00165f. View

13.

Croue V, Goeb S, Szaloki G, Allain M, Salle M . Reversible Guest Uptake/Release by Redox-Controlled Assembly/Disassembly of a Coordination Cage. Angew Chem Int Ed Engl. 2015; 55(5):1746-50. DOI: 10.1002/anie.201509265. View

14.

Samantray S, Krishnaswamy S, Chand D . Self-assembled conjoined-cages. Nat Commun. 2020; 11(1):880. PMC: 7021905. DOI: 10.1038/s41467-020-14703-4. View

15.

Wang L, Song B, Khalife S, Li Y, Ming L, Bai S . Introducing Seven Transition Metal Ions into Terpyridine-Based Supramolecules: Self-Assembly and Dynamic Ligand Exchange Study. J Am Chem Soc. 2020; 142(4):1811-1821. PMC: 7375339. DOI: 10.1021/jacs.9b09497. View

16.

Wei S, Pan M, Fan Y, Liu H, Zhang J, Su C . Creating coordination-based cavities in a multiresponsive supramolecular gel. Chemistry. 2015; 21(20):7418-27. DOI: 10.1002/chem.201406517. View

17.

Yu G, Jie K, Huang F . Supramolecular Amphiphiles Based on Host-Guest Molecular Recognition Motifs. Chem Rev. 2015; 115(15):7240-303. DOI: 10.1021/cr5005315. View

18.

Yamashina M, Tanaka Y, Lavendomme R, Ronson T, Pittelkow M, Nitschke J . An antiaromatic-walled nanospace. Nature. 2019; 574(7779):511-515. DOI: 10.1038/s41586-019-1661-x. View

19.

Jansze S, Severin K . Palladium-Based Metal-Ligand Assemblies: The Contrasting Behavior upon Addition of Pyridine or Acid. J Am Chem Soc. 2019; 141(2):815-819. DOI: 10.1021/jacs.8b12738. View

20.

Diaz-Moscoso A, Ballester P . Light-responsive molecular containers. Chem Commun (Camb). 2017; 53(34):4635-4652. DOI: 10.1039/c7cc01568b. View