A Lantern‐Shaped Pd(II) Cage Constructed from Four Different Low‐Symmetry Ligands with Positional and Orientational Control: An Ancillary Pairings Approach DOI Creative Commons
Dan Preston, Jack D. Evans

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(49)

Published: Oct. 11, 2023

Abstract One of the key challenges metallo‐supramolecular chemistry is to maintain ease self‐assembly but, at same time, create structures increasingly high levels complexity. In palladium(II) quadruply stranded lantern‐shaped cages, this has been achieved through either 1) formation heteroleptic (multi‐ligand) assemblies, or 2) homoleptic assemblies from low‐symmetry ligands. Heteroleptic cages formed ligands, a hybid these two approaches, would add an additional rich level complexity but no examples have reported. Here we use system ancillary complementary ligand pairings termini cage ligands target assemblies: pairs can only interact (through coordination single Pd(II) metal ion) between in cis position on cage. Complementarity each pair (and orthogonality other pairs) controlled by denticity (tridentate monodentate bidentate bidentate) and/or hydrogen‐bonding capability (AA DD AD DA). This allows positional and orientational control over with different sites. By using approach, successfully used synthesise complex including example four

Language: Английский

Cage‐To‐Cage Transformations in Self‐Assembled Coordination Cages Using “Acid/Base” or “Guest Binding‐Induced Strain” as Stimuli DOI
Vellaiyadevan Sivalingam,

Minaz Parbin,

Shobhana Krishnaswamy

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 3, 2024

Abstract Controlling supramolecular systems between different functional forms by utilizing acids/bases as stimuli is a formidable challenge, especially where labile coordination bonds are involved. A pair of acid/base responsive, interconvertible 1,5‐enedione/pyrylium based Pd 2 L 4 ‐type cages prepared that exhibit differential guest binding abilities towards disulfonates varied sizes. three‐state switch has been achieved, (i) weakly coordinating base induced cage‐to‐cage transformation in the first step, (ii) strongly triggered cage disassembly second and (iii) third step shows acid(strong) promoted generation initial cage, thereby completing cycle. To our surprise, specific disulfonate facilitated transformations inducing strain on assembly opening pyrylium rings cage. Through competitive study, we demonstrated superior capability octacationic pyrylium‐based over similar‐sized tetracationic These results provide reliable approach to reversibly modulate properties acid/base‐responsive self‐assembled cages.

Language: Английский

Citations

9
Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering** DOI Creative Commons
Paulina Molinska, Andrew Tarzia, Louise Male

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(51)

Published: Oct. 27, 2023

Metal-organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low-symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomer libraries. We set out to investigate use primary coordination-sphere engineering (CSE) bias selectivity within homo- heteroleptic Pd

Language: Английский

Citations

21
A Lantern‐Shaped Pd(II) Cage Constructed from Four Different Low‐Symmetry Ligands with Positional and Orientational Control: An Ancillary Pairings Approach DOI Creative Commons
Dan Preston, Jack D. Evans

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 11, 2023

One of the key challenges metallo-supramolecular chemistry is to maintain ease self-assembly but, at same time, create structures increasingly high levels complexity. In palladium(II) quadruply stranded lantern-shaped cages, this has been achieved through either 1) formation heteroleptic (multi-ligand) assemblies, or 2) homoleptic assemblies from low-symmetry ligands. Heteroleptic cages formed ligands, a hybid these two approaches, would add an additional rich level complexity but no examples have reported. Here we use system ancillary complementary ligand pairings termini cage ligands target assemblies: pairs can only interact (through coordination single Pd(II) metal ion) between in cis position on cage. Complementarity each pair (and orthogonality other pairs) controlled by denticity (tridentate monodentate bidentate bidentate) and/or hydrogen-bonding capability (AA DD AD DA). This allows positional and orientational control over with different sites. By using approach, successfully used synthesise complex including example four

Language: Английский

Citations

20
Palladium-based coordination cages as dynamic crosslinks in acrylamide hydrogels DOI Creative Commons
Chaolei Hu,

Damien W. Chen,

Sylvain Sudan

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Hydrogels with Pd n L 2 -type junctions can be obtained by photoinitiated copolymerization of palladium cages acrylamide monomers in water. The dynamic nature the cage crosslinks allows for an anion-induced switch network topology.

Language: Английский

Citations

0
A Dynamic Covalent Approach to [PtnL2n]2n+ Cages DOI
Quinn V. C. van Hilst, Aston C. Pearcy, Dan Preston

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(32), P. 4302 - 4305

Published: Jan. 1, 2024

A dynamic covalent approach was exploited to generate a family of homometallic [Pt n L 2 ] + cage (predominantly 4 4+ systems) architectures.

Language: Английский

Citations

2
Substrate Selectivity Imparted by Self‐Assembled Molecular Containers and Catalysts DOI Open Access
Tommaso Lorenzetto, Francesca Bordignon,

Luca Munarin

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(10)

Published: July 19, 2023

Recent trends in catalysis are devoted to mimicking some peculiar features of enzymes like site selectivity, through functional group recognition, and substrate recognition the entire surface substrate. The latter is a specific feature that seldomly present homogeneous catalysis. Supramolecular catalysis, thanks self-assembly simple subunits, enables creation cavities surfaces whose confinement effects drive preferential binding among others with consequent selectivity. topic an emerging field exploits phenomena discriminate reagents based on their size shape. This review deals this cutting-edge research covering examples supramolecular self-assembled molecular containers catalysts operating organic as well aqueous media, special emphasis for catalytic systems dealing direct competitive experiments involving two or more substrates.

Language: Английский

Citations

5
Interaction of dinuclear Co(III) cylinders with higher-order DNA structures DOI
Jaroslav Malina, James D. Crowley, Viktor Brabec

et al.

Chemico-Biological Interactions, Journal Year: 2024, Volume and Issue: 395, P. 111031 - 111031

Published: May 1, 2024

Language: Английский

Citations

1
Orientational Compatibility Modulation of Ligands in Low‐Symmetry Multi‐Cavity Discrete Coordination Cages by Neighbouring Cage Participation DOI Open Access
Ashish Kumar, Shobhana Krishnaswamy, Dillip Kumar Chand

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 19, 2024

Complexation of Pd(II) with a designer unsymmetrical bis-monodentate ligand (2 : 4 ratio) yielded specific Pd

Language: Английский

Citations

1
Diastereoselective Self‐Assembly of Low‐Symmetry PdnL2n Nanocages through Coordination‐Sphere Engineering** DOI Creative Commons
Paulina Molinska, Andrew Tarzia, Louise Male

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(51)

Published: Oct. 27, 2023

Abstract Metal‐organic cages (MOCs) are popular host architectures assembled from ligands and metal ions/nodes. Assembling structurally complex, low‐symmetry MOCs with anisotropic cavities can be limited by the formation of statistical isomer libraries. We set out to investigate use primary coordination‐sphere engineering (CSE) bias selectivity within homo‐ heteroleptic Pd n L 2 cages. Unexpected differences in selectivities between alternative donor groups led us recognise significant impact second coordination sphere on stabilities. From this, molecular‐level insight into origins cis trans diastereoisomers was gained, highlighting importance both host–guest host‐solvent interactions, addition ligand design. This detailed understanding allows precision MOC assemblies without wholesale redesign framework, fundamentally provides a theoretical scaffold for development stimuli‐responsive, shape‐shifting MOCs.

Language: Английский

Citations

2
Cage‐To‐Cage Transformations in Self‐Assembled Coordination Cages Using “Acid/Base” or “Guest Binding‐Induced Strain” as Stimuli DOI
Vellaiyadevan Sivalingam,

Minaz Parbin,

Shobhana Krishnaswamy

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(23)

Published: April 3, 2024

Abstract Controlling supramolecular systems between different functional forms by utilizing acids/bases as stimuli is a formidable challenge, especially where labile coordination bonds are involved. A pair of acid/base responsive, interconvertible 1,5‐enedione/pyrylium based Pd 2 L 4 ‐type cages prepared that exhibit differential guest binding abilities towards disulfonates varied sizes. three‐state switch has been achieved, (i) weakly coordinating base induced cage‐to‐cage transformation in the first step, (ii) strongly triggered cage disassembly second and (iii) third step shows acid(strong) promoted generation initial cage, thereby completing cycle. To our surprise, specific disulfonate facilitated transformations inducing strain on assembly opening pyrylium rings cage. Through competitive study, we demonstrated superior capability octacationic pyrylium‐based over similar‐sized tetracationic These results provide reliable approach to reversibly modulate properties acid/base‐responsive self‐assembled cages.

Language: Английский

Citations

0