A Combined Experimental and Computational Exploration of Heteroleptic cis‐Pd2L2L’2 Coordination Cages through Geometric Complementarity DOI Creative Commons
Andrew Tarzia,

Wentao Shan,

Víctor Posligua

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 27, 2024

Abstract Heteroleptic (mixed‐ligand) coordination cages are of interest as host systems with more structurally and functionally complex cavities than homoleptic architectures. The design heteroleptic cages, however, is far from trivial. In this work, we experimentally probed the self‐assembly Pd(II) ions binary ligand combinations in a combinatorial fashion to search for new cis ‐Pd 2 L L’ cages. A hierarchy computational analyses was then applied these aim elucidating key factors rationalising outcomes. Simple inexpensive geometric were shown be effective identifying complementary pairs. Preliminary results demonstrated viability relatively rapid semi‐empirical calculations predicting topology thermodynamically favoured assemblies rigid ligands, whilst flexible proved challenging. Stemming this, challenges identified future work developing forecasting tools self‐assembled metallo‐supramolecular systems.

Language: Английский

Construction of BODIPY-based triangular metallacycles with tunable photosensitization efficiency DOI
Peipei Jia,

Yi-Xiong Hu,

Zhen‐Chen Lou

et al.

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 110835 - 110835

Published: Jan. 1, 2025

Language: Английский

Citations

0
Guest Segregation in Heteromeric Multicage Systems DOI
Élie Benchimol,

Andrea Rivoli,

Michele Kabiri

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Dynamically interconvertible metallo-supramolecular multicomponent assemblies, coexisting orthogonally in solution, serve as simplified mimics for complex networks found biological systems. Building on recent advances controlling the nonstatistical self-assembly of heteroleptic coordination cages and heteromeric completive self-sorting, i.e., coformation multiple low-symmetry we herein describe first instance emerging functionality from a multicage system. In particular, one cage coexists equilibrium with or two different homoleptic cages, each capable preferentially encapsulating out three guests within their cavities. Guest segregation occurs under thermodynamic control can be reached following several distinct paths. Each pathway involves sequential transformations, eventually leading to same outcome. We that most mixture components (three ligands, guests, plus palladium cations) always yields an ordered, pathway-independent final state host–guest species, thus representing case simplexity self-sorted This study forms basis expanding scope dynamic transformation processes implemented Together incorporation stimuli-responsive elements other functionality, populations bioinspired applications controllable compound separation schemes, compartmentalized cascade reactions, multistep (even bifurcated) molecular information processing will become accessible.

Language: Английский

Citations

0
Deciphering the mechanism of structural transformation between Pd3L6 and Pd4L8 metal-organic cages DOI

Xian‐Chao Zhou,

Y. Tan,

Ying-Ying Ge

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Language: Английский

Citations

0
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
Self-assembly, interlocking, interconversion and anion-binding catalysis in phenoxazine-based Pd2L4 and Pd4L8 coordination cages DOI Creative Commons

Qiong‐Yan Hong,

Bin Huang,

Meng‐Xiang Wu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 13, 2025

Interpenetration is a phenomenon frequently encountered in self-assembled Pd2L4-type coordination cages, while the mechanism of interpenetration process remains unclear. Here we show synthesis and solvent-mediated interconversion highly soluble phenoxazine-based monomeric cage 1 corresponding interlocked dimer 2. We succeed isolation single-crystal structure analysis both 2 with same guest anion by changing solvents utilized self-assembly. The monomeric-to-dimeric conversion occurs heating weakly coordinating solvents, dimeric-to-monomeric takes place through disassembly reassembly strongly at low concentration or addition/removal competing ligand. may be driven distinct thermodynamic stabilities different solvents. Additionally, Cl– anions template because strong chloride binding affinity which could serve as an anion-binding catalyst for C–Cl bond cleavage. While cages tend to form dimers, characterization its very challenging. Herein, authors report dimer.

Language: Английский

Citations

0
Design and Synthesis of a Cluster-Based Supramolecular Reaction Pump for the Efficient Catalysis of Amination Reactions DOI
Yun‐Hu Deng, Brendan F. Abrahams, Jian‐Ping Lang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: May 16, 2025

Although discrete self-assembled cage compounds with single-metal centers mimicking natural bioreactors for catalysis have been extensively investigated, studies on those multimetal active centers, i.e., cluster (CACs), less explored. Herein, we present the design and synthesis of a novel cluster-based supramolecular reaction pump (CSRP-1) featuring four CACs that facilitate catalysis. CSRP-1 holds cationic tetrahedral structure, comprising WS3Cu3 clusters, each positioned at one vertex interconnected by dipyridyl linkers. Substrates, including aryl iodides or primary secondary amines, enter cavity replacing N,N-dimethylformamide through weak Cu···I/N interactions. This leverages coordinatively unsaturated Cu within CAC to activate substrates, resulting in efficient catalytic amination. works like dynamic pump, upon completion reaction, amine product is expelled from cavity, allowing cycle repeat maintained efficiency. Theoretical calculations complement experimental findings, providing key insights into mechanism synergistic role clusters work offers new paradigm broad applicability various organic reactions.

Language: Английский

Citations

0
Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo‐Divergent Semi‐Hydrogenation of Alkynes DOI
Wei Zhong, Xu Jing, Zhao Song

et al.

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

Published: Nov. 6, 2024

Abstract An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking off‐on‐off selectivity in semi‐hydrogenation of alkynes. Water serves critical regulator, modulating catalyst states, reaction rates, and endpoints. The choice solvent influences activity host–guest binding types homogeneous heterogeneous catalysis, effectively modifying steps involved Z → E isomerization during Kinetic inhibition experiments indicate that mimics activation characteristics enzymes towards substrates, enabling selective transformations within confined environment. utility this switchable cage‐confined catalysis demonstrated synthesis modification complex biologically active molecules with controllable / selectivity. This work sheds light on design control artificial counterparts enzymes, offering fundamental insights into factors influencing biological macromolecules.

Language: Английский

Citations

2
Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo‐Divergent Semi‐Hydrogenation of Alkynes DOI Open Access
Wei Zhong, Jing Xu, Song Zhao

et al.

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

Published: Nov. 6, 2024

Abstract An enzyme‐mimicking catalytic system has been established using a singular palladium‐based octahedral cage as the supramolecular reactor, deftly unlocking off‐on‐off selectivity in semi‐hydrogenation of alkynes. Water serves critical regulator, modulating catalyst states, reaction rates, and endpoints. The choice solvent influences activity host–guest binding types homogeneous heterogeneous catalysis, effectively modifying steps involved Z → E isomerization during Kinetic inhibition experiments indicate that mimics activation characteristics enzymes towards substrates, enabling selective transformations within confined environment. utility this switchable cage‐confined catalysis demonstrated synthesis modification complex biologically active molecules with controllable / selectivity. This work sheds light on design control artificial counterparts enzymes, offering fundamental insights into factors influencing biological macromolecules.

Language: Английский

Citations

0
A Combined Experimental and Computational Exploration of Heteroleptic cis‐Pd2L2L’2 Coordination Cages through Geometric Complementarity DOI Creative Commons
Andrew Tarzia,

Wentao Shan,

Víctor Posligua

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 27, 2024

Abstract Heteroleptic (mixed‐ligand) coordination cages are of interest as host systems with more structurally and functionally complex cavities than homoleptic architectures. The design heteroleptic cages, however, is far from trivial. In this work, we experimentally probed the self‐assembly Pd(II) ions binary ligand combinations in a combinatorial fashion to search for new cis ‐Pd 2 L L’ cages. A hierarchy computational analyses was then applied these aim elucidating key factors rationalising outcomes. Simple inexpensive geometric were shown be effective identifying complementary pairs. Preliminary results demonstrated viability relatively rapid semi‐empirical calculations predicting topology thermodynamically favoured assemblies rigid ligands, whilst flexible proved challenging. Stemming this, challenges identified future work developing forecasting tools self‐assembled metallo‐supramolecular systems.

Language: Английский

Citations

0