Synthesis of a Pd2L4 Hydrazone Molecular Cage Through Multiple Reaction Pathways DOI Open Access
Giovanni Montà-González, Ramón Martínez‐Máñez, Vicente Martí‐Centelles

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(22), P. 11861 - 11861

Published: Nov. 5, 2024

Molecular cages are preorganized molecules with a central cavity, typically formed through the reaction of their building blocks chemical bonds. This requires, in most cases, forming and breaking reversible bonds during cage formation pathway for error correction to drive product. In this work, we focus on both Pd-ligand hydrazone implemented structure Pd

Language: Английский

Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages DOI

Fenglei Qiu,

Xinting Zhang,

Wenjing Wang

et al.

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

Published: March 2, 2025

The development of new chiral building blocks for constructing complex architectures, such as macrocycles and cages, is both crucial challenging. Although concave-shaped calixarenes have been established versatile the synthesis cage compounds, there are no reports on cages constructed from calix[4]arene derivatives. Herein, we present a straightforward effective method gram-scale member macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As proof concept, functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via Duff reaction to construct porous organic (CPOCs) using polyamine synthons. Specifically, employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine tris(4-aminophenyl)amine, assemble with PC[4]ACHO resulting in [2 + 4] lantern-shaped [6 8] truncated octahedral CPOCs, respectively. These structures unambiguously characterized by single-crystal X-ray diffraction circular dichroism (CD) spectroscopy. Notably, CPOCs exhibit internal diameters approximately 3.1 nm, cavity volume around 5300 Å3, high specific surface areas up 1300 m2 g-1 after desolvation, making them among largest reported. Additionally, investigations their sensing performance demonstrate that PC[4]A-based enable enantioselective recognition amino acids This work strongly suggests PC[4]A can serve an excellent block rational design materials practical applications.

Language: Английский

Citations

1
A Perspective on Carbon–Carbon Diradical-Mediated Dynamic Covalent Synthesis of Organic Macrocycles and Their Emerging Functions DOI
R. Saravanan,

Infantia Mirin N,

Sankarasekaran Shanmugaraju

et al.

Crystal Growth & Design, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

A biological self-assembly of organized supramolecular structures and functional materials has emerged as a significant research focus in recent decades. Different strategies have been proposed successfully adopted for engineering complex structures. Among others, substantial progress made using dynamic covalent chemistry (DCC) to generate with sophisticated properties. This Perspective elaborates on the role carbon–carbon (C–C)-based diradical-based DCC self-assembly. It provides an in-depth discussion structural aspects C–C bonds discrete oligomer formation including dimers, trimers, tetramers, hexameric Early sections survey critical factors contributing longevity stability radical systems influences substitution diradicals into dimers or macrocycles. Significant attention given characteristics diradical impact hydrogen π–π interactions configurations self-assembled The latter part this article properties applications DCC-mediated primary objectives review are (i) present detailed analysis benefits associated diradical-mediated (ii) investigate their

Language: Английский

Citations

0
Chiral Pt(II)–V(V) Bimetallic Cages and Guest-Induced Allosteric Regulation of Catalytic Asymmetric Sulfoxidation DOI Creative Commons
Yue Jiang, Yawei Liu, Gen Li

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Flexible metal–organic cages can provide confined active metal sites and show promise in mimicking metalloenzymes. In this study, we synthesized two flexible chiral bimetallic coordination cages, [(PEt3)6Pt3(R,R,R-VL)2]6+ its enantiomer, through the self-assembly of platinum(II) precursors with enantiopure tripodal vanadium(V) complexes bearing pendant pyridyl groups (VL). The guest binding camphorsulfonate anions, concomitant changes cage conformation. catalytic properties for oxidizing thioethers into sulfoxides were investigated comparison a simple complex. While complex, either alone or along camphorsulfonate, does not any enantioselectivity, enables enantioselective oxidation even though enantiomeric excess is low. stereoselectivity significantly improved after introduced to cage. acts like an allosteric effector enzymes modulate conformation local microenvironment around site favor induction. This work highlights potentials leveraging cage-confined host–guest interactions advancing supramolecular asymmetric catalysis.

Language: Английский

Citations

0
Macrocyclic arene-based metal-organic cages DOI
Yujuan Zhou, Jie Yang, Kecheng Jie

et al.

Coordination Chemistry Reviews, Journal Year: 2025, Volume and Issue: 539, P. 216726 - 216726

Published: April 25, 2025

Language: Английский

Citations

0
Controlled Assembly of [3+6] and [4+8] Porous Organic Cages for Rapid Removal of Iodide from Water DOI

Guoshi Zhang,

Jiajia Sheng, Wenjing Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

Comprehensive Summary Research into controlling the self‐assembly of discrete porous organic cages (POCs) with specific geometries and functions is difficult, but important for understanding their structure‐property relationship, as well behavior in supramolecular chemistry. Herein, we report two POCs based on same tetraformyl‐functionalized calix[4]resorcinarene (C4RACHO) 2,4‐diaminophenol dihydrochloride (DAP) building blocks, including a [3+6] triangular prism ( CPOC‐201‐OH ) [4+8] square CPOC‐401‐OH ), determined by single X‐ray crystallographic analysis. Both exhibit large intrinsic cavities, rich oxygen sites, high porosity Brunauer–Emmett–Teller (BET) surface areas up to 966 m 2 ·g –1 . Owing such virtues, both can effectively capture iodine aqueous media removal rate > 99% within min.

Language: Английский

Citations

0
Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages DOI Creative Commons
Keith G. Andrews

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 421 - 443

Published: Feb. 24, 2025

The bespoke environments in enzyme active sites can selectively accelerate chemical reactions by as much 1019. Macromolecular and supramolecular chemists have been inspired to understand mimic these accelerations selectivities for applications catalysis sustainable synthesis. Over the past 60+ years, mimicry strategies evolved with changing interests, understanding, synthetic advances but, ubiquitously, research has focused on use of a molecular "cavity". activities different cavities vary subset features available particular cavity type. Unsurprisingly, without access mimics able encompass more/all functional sites, examples cavity-catalyzed processes demonstrating enzyme-like rate remain rare. This perspective will briefly highlight some key traditional catalysis, type, order contextualize recent development robust organic cage catalysts, which exploit stability, functionality, reduced symmetry enable promising catalytic modes.

Language: Английский

Citations

0
Metal-free porphyrin porous organic cage for efficient iodine capture DOI
Zhixuan Wang, Juanjuan Li,

Ziwei Du

et al.

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 161326 - 161326

Published: March 1, 2025

Language: Английский

Citations

0
Synergistic regulation of metal–organic cage architectures via temperature- and solvent-driven atropisomerism DOI Creative Commons
Jiaqi Liang,

Li‐Jun Peng,

Kelin Zhu

et al.

Proceedings of the National Academy of Sciences, Journal Year: 2025, Volume and Issue: 122(19)

Published: May 8, 2025

Regulating multistimulus responses in artificial systems remains a challenge smart material development. We present versatile chemical switching system that precisely controls the self-assembly of metal–organic cages via temperature and solvent changes. The key component, cyclo[2](1,3-(4,6-dimethyl)benzene) (4-pyridine)[6](1,3-(4,6-dimethyl)benzene) ( CP2 ), was generated as three atropisomers 1 , 2 3 ) with C s 2v symmetries. Thermally, metastable isomers convert into stable isomer which reacts Pd 2+ to form specific molecular cages. Depending on solvent, either rectangular M L 5′ 5 1,4-dioxane or hexagonal 6 1,1′,2,2′-tetrachloroethane. dictates cage type enables reversible transformation between . Additionally, ′, formed from can switch other types (i.e., depending conditions. This multipathway offers precise strategy for controlling materials.

Language: Английский

Citations

0
To a mechanical model of synthetic catch-bonds DOI Creative Commons
Wolfgang Quapp, Josep María Bofill, Kerim C. Dansuk

et al.

Journal of Mathematical Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

Language: Английский

Citations

0
Synthesis of a Pd2L4 Hydrazone Molecular Cage Through Multiple Reaction Pathways DOI Open Access
Giovanni Montà-González, Ramón Martínez‐Máñez, Vicente Martí‐Centelles

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(22), P. 11861 - 11861

Published: Nov. 5, 2024

Molecular cages are preorganized molecules with a central cavity, typically formed through the reaction of their building blocks chemical bonds. This requires, in most cases, forming and breaking reversible bonds during cage formation pathway for error correction to drive product. In this work, we focus on both Pd-ligand hydrazone implemented structure Pd

Language: Английский

Citations

0