Gram-scale synthesis of a covalent nanocage that preserves the redox properties of encapsulated fullerenes DOI Creative Commons
Daniel A. Rothschild, William P. Kopcha, Aaron Tran

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(18), P. 5325 - 5332

Published: Jan. 1, 2022

Discrete nanocages provide a way to solubilize, separate, and tune the properties of fullerenes, but these 3D receptors cannot usually be synthesized easily from inexpensive starting materials, limiting their utility. Herein, we describe first fullerene-binding nanocage (Cage4+) that can made efficiently on gram scale. Cage4+ was prepared in up 57% yield by formation pyridinium linkages between complemantary porphyrin components are themselves readily accessible. binds C60 C70 with large association constants (>108 M-1), thereby solubilizing fullerenes polar solvents. Fullerene redox-properties were subsequently investigated across multiple charge states host-guest complexes. Remarkably, neutral singly reduced bind similar strengths, leaving 0/1- redox couples minimally perturbed fully reversible, whereas other hosts substantially alter fullerenes. Thus, C60@Cage4+ C70@Cage4+ may useful as solubilized fullerene derivatives preserve inherent electron-accepting electron-transfer capabilities Fulleride dianions also found strongly Cage4+, while further reduction is centered host, leading lowered fulleride guest case C602-.

Language: Английский

Beyond Platonic: How to Build Metal–Organic Polyhedra Capable of Binding Low-Symmetry, Information-Rich Molecular Cargoes DOI Creative Commons
Charlie T. McTernan, Jack A. Davies, Jonathan R. Nitschke

et al.

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(11), P. 10393 - 10437

Published: April 18, 2022

The field of metallosupramolecular chemistry has advanced rapidly in recent years. Much work this area focused on the formation hollow self-assembled metal-organic architectures and exploration applications their confined nanospaces. These discrete, soluble structures incorporate metal ions as 'glue' to link organic ligands together into polyhedra.Most employed thus far have been highly symmetrical, these easiest prepare. Such high-symmetry contain pseudospherical cavities, so typically bind roughly spherical guests. Biomolecules high-value synthetic compounds are rarely isotropic, highly-symmetrical species. To bind, sense, separate, transform such substrates, new, lower-symmetry, cages needed. Herein we summarize approaches, which taken form first draft a handbook for design higher-complexity, architectures.

Language: Английский

Citations

197

Highly Emissive Perylene Diimide-Based Metallacages and Their Host–Guest Chemistry for Information Encryption DOI

Yali Hou,

Zeyuan Zhang,

Shuai Lu

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(44), P. 18763 - 18768

Published: Oct. 21, 2020

Here we report two highly emissive perylene diimide (PDI)-based metallacages and explore their complexation with polycyclic aromatic hydrocarbons, such as pyrene, triphenylene, perylene. The fluorescence quantum yields of exceed 90% binding constants can reach high 2.41 × 104 M-1 in acetonitrile. These features enable further tuning the emission host-guest complexes to obtain white-light based on complementary orange blue Moreover, owing huge differences solution solid state, are successfully employed for information encryption. This study offers a general approach construction explores application

Language: Английский

Citations

154

Self-Assembled Metallacage with Second Near-Infrared Aggregation-Induced Emission for Enhanced Multimodal Theranostics DOI
Yi Qin, Xiaohong Chen,

Yixiong Gui

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12825 - 12833

Published: July 5, 2022

The construction of supramolecular coordination complexes (SCCs) featuring prominent cancer theranostic functions is an appealing yet significantly challenging task. In this study, we rationally designed and facilely constructed a prism-like metallacage C-DTTP with efficient fluorescence emission in the second near-infrared (NIR-II) region through assembly aggregation-induced emission-active four-arm ligand 90° Pt acceptors Pt(PEt3)2(OTf)2. held longest maximum wavelength (1005 nm) compared those previously reported SCCs up to now exhibited both high photothermal conversion efficiency (39.3%) superior reactive oxygen species generation behavior precursor ligand. vitro vivo assessments demonstrated that metallacage-loaded nanoparticles excellent biocompatibility stability were capable simultaneously affording precise tumor diagnosis complete elimination by means NIR-II fluorescence/photothermal dual imaging-guided photodynamic/photothermal synergistic therapy.

Language: Английский

Citations

127

Recent advances in supramolecular fullerene chemistry DOI Creative Commons
Xingmao Chang, Youzhi Xu, Max von Delius

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 47 - 83

Published: Oct. 18, 2023

We review recent work at the interface of supramolecular chemistry and fullerene chemistry. focus on selective functionalization, host–guest chemistry, non-covalent dyads, mechanically interlocked architectures 2D/3D assemblies.

Language: Английский

Citations

91

Molecular Barrels as Potential Hosts: From Synthesis to Applications DOI
Ranit Banerjee, Debsena Chakraborty, Partha Sarathi Mukherjee

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 7692 - 7711

Published: March 28, 2023

Self-assembled discrete molecular architectures that show selective recognition within their internal cavities are highly desirable. Such hosts often guest through several noncovalent interactions. This emulates the activity of naturally occurring enzymes and proteins. Research in formation 3D cages different shapes sizes has progressed rapidly since development coordination-driven self-assembly dynamic covalent chemistry. find applications catalysis, stabilization metastable molecules, purification isomeric mixtures via encapsulation, even biomedical applications. Most these stem from ability host to bind guests strongly a fashion, providing suitable environment for perform functions. Molecular having closed with small windows either poor encapsulation or inhibit easy release while those wide open structures fail form stable host-guest complexes. In this context, barrels obtained by metal-ligand/covalent bond techniques possess optimized architectures. With hollow-walled cavity two large openings, satisfy structural requirements many perspective, we will discuss detail synthetic strategies obtaining barrel-like employing coordination interactions, structure-based classification, storing transient separation chemicals, photoinduced antibacterial activity. We aim highlight advantages over other efficiently carrying out functions new

Language: Английский

Citations

64

A Self‐Assembled Palladium(II) Barrel for Binding of Fullerenes and Photosensitization Ability of the Fullerene‐Encapsulated Barrel DOI
Prioti Choudhury Purba,

Manoranjan Maity,

S. Bhattacharyya

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(25), P. 14109 - 14116

Published: April 9, 2021

Fullerene extracts obtained from fullerene soot lack their real application due to poor solubility in common solvents and difficulty purification. Encapsulation of these a suitable host is an important approach address issues. We present new Pd6 barrel (1), which composed three 1,4-dihydropyrrolo[3,2-b]pyrrole panels, clipped through six cis-PdII acceptors. Large open windows cavity make it efficient for large guest. Favorable interactions between the ligand (C60 C70 ) allows encapsulate efficiently. Thorough investigation reveals that 1 has stronger binding affinity towards over C60 , resulting predominant extraction mixture two. Finally, encapsulated barrels ⊂1 were found be visible-light-induced singlet oxygen generation. Such preferential photosensitizing ability are noteworthy.

Language: Английский

Citations

81

Molecular Cages Self‐Assembled by Imine Condensation in Water DOI
Lei Ye, Qiong Chen, Peiren Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(9), P. 4705 - 4711

Published: Nov. 30, 2020

Self-assembly by imine condensation in aqueous media is a formidable task because of the labile nature imines presence water. Here, taking advantage multivalence and ligand preorganization, basket-shaped triscationic cage molecules are self-assembled high yields both water organic solvent, condensing hexaformyl bisamine. These cages, especially chiral ones, stable or inert solution, that is, no decomposition was observed upon dilution, precipitation, exposure to competitive amines aldehydes. Such water-compatibility allows hosts take hydrophobic effect accommodate guests. The S-23+ selectively binds distinguishes one two enantiomers, opening up opportunities for applications such as compound separation. Chiral narcissistic self-sorting sergeants-and-soldiers effects occur during formation when amino precursors involved self-assembly.

Language: Английский

Citations

80

A Redox-Active Supramolecular Fe4L6 Cage Based on Organic Vertices with Acid–Base-Dependent Charge Tunability for Dehydrogenation Catalysis DOI
Yu‐Lin Lu, Jiaqi Song,

Yu-Han Qin

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8778 - 8788

Published: May 4, 2022

Supramolecular cage chemistry is of lasting interest because, as artificial blueprints natural enzymes, the self-assembled structures not only provide substrate-hosting biomimetic environments but also can integrate active sites in confined nanospaces for function synergism. Herein, we demonstrate a vertex-directed organic-clip chelation assembly strategy to construct metal–organic Fe4L68+ (MOC-63) incorporating 12 imidazole proton donor–acceptor motifs and four redox-active Fe centers an octahedral coordination nanospace. Different from regular supramolecular cages assembled with metal vertices, MOC-63 comprises six ditopic ligands vertices tris-chelating Fe(N∩N)3 moieties faces, thus improving its acid, base, redox robustness by virtue cage-stabilized dynamics solution. Improved dehydrogenation catalysis 1,2,3,4-tetrahydroquinoline derivatives accomplished owing effect that synergizes multiple radical species expedite intermediate conversion multistep reactions cage-confined The acid–base buffering play vital role modulating total charge state resist pH variation tune solubility among varied solvents, thereby enhancing reaction acceleration acidic conditions rendering facile recycling catalytic process.

Language: Английский

Citations

65

One‐Pot and Shape‐Controlled Synthesis of Organic Cages DOI
Xiang Zhao, Yue Liu, Zhiyuan Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(33), P. 17904 - 17909

Published: May 26, 2021

Abstract Organic cages are fascinating because of their well‐defined 3D cavities, excellent stability, and accessible post‐modification. However, the synthesis is normally realized by fragment coupling approach in low yields. Herein, we report one‐pot, gram‐scale shape‐controlled two covalent organic (box‐shaped [4]cage triangular prism‐shaped [2]cage) yields 46 % 52 %, involving direct condensation 1,3,5‐tris(2,4‐dimethoxyphenyl)benzene monomer with paraformaldehyde isobutyraldehyde, respectively. The can convert into high‐yielding per‐hydroxylated analogues. [2]cage be utilized as gas chromatographic stationary phase for high‐resolution separation benzene/cyclohexane toluene/methylcyclohexane. By changing central moiety and/or aldehyde, this synthetic method would have potential to a general strategy access diverse tunable shape, size, electronic properties.

Language: Английский

Citations

63

Photo-assisted charge/discharge Li-organic battery with a charge-separated and redox-active C60@porous organic cage cathode DOI
Xiang Zhang, Kongzhao Su, Aya Gomaa Abdelkader Mohamed

et al.

Energy & Environmental Science, Journal Year: 2021, Volume and Issue: 15(2), P. 780 - 785

Published: Dec. 22, 2021

A charge-separated and redox-active C 60 @porous organic cage (C @POC) compound was synthesized to act as the cathode in a photo-assisted Li-organic battery, which enables efficient solar electrochemical energy conversion storage.

Language: Английский

Citations

60