Recent advances in supramolecular fullerene chemistry

Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 47 - 83

Опубликована: Окт. 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.

Язык: Английский

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Guest‐Regulated Generation of Reactive Oxygen Species from Porphyrin‐Based Multicomponent Metallacages for Selective Photocatalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 2, 2024

Abstract The development of novel materials for highly efficient and selective photocatalysis is crucial their practical applications. Herein, we employ the host‐guest chemistry porphyrin‐based metallacages to regulate generation reactive oxygen species further use them photocatalytic oxidation benzyl alcohols. Upon irradiation, sole metallacage ( 6 ) can generate singlet 1 O 2 effectively via excited energy transfer, while its complex with C 70 ⊃C opens a pathway electron transfer promote formation superoxide anion (O ⋅ − ), producing both . addition 4,4′‐bipyridine (BPY) forms more stable ⊃BPY) coordination Zn‐porphyrin faces BPY, which drives fullerenes out cavities restores ability generation. Therefore, alcohols are oxidized into aldehydes upon irradiation in presence or ⊃BPY, they benzoic acids when employed as photosensitizing agent. This study demonstrates strategy that utilizes photooxidation reactions, could utilization related complexes

Язык: Английский

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Light‐Responsive Supramolecular Liquid‐Crystalline Metallacycle for Orthogonal Multimode Photopatterning

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(4)

Опубликована: Ноя. 15, 2023

Abstract The development of multimode photopatterning systems based on supramolecular coordination complexes (SCCs) is considerably attractive in chemistry and materials science, because SCCs can serve as promising platforms for the incorporation multiple functional building blocks. Herein, we report a light‐responsive liquid‐crystalline metallacycle that constructed by coordination‐driven self‐assembly. By exploiting its fascinating liquid crystal features, bright emission properties, facile photocyclization capability, unique system with spatially‐controlled fluorescence‐resonance energy transfer (FRET) built through introduction photochromic spiropyran derivative, which led to realization first example orthogonal three‐modes, namely holography, fluorescence, photochromism.

Язык: Английский

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Supramolecular Architectures Bearing Half-Sandwich Iridium- or Rhodium-Based Carboranes: Design, Synthesis, and Applications

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(36), С. 19440 - 19457

Опубликована: Авг. 29, 2023

The utilization of carboranes in supramolecular chemistry has attracted considerable attention. unique spatial configuration and weak interaction forces can help to explore the properties complexes, particularly via host–guest chemistry. Additionally, certain difficulties encountered carborane development─such as controlled B–H bond activation─can be overcome by judiciously selecting metal centers their adjacent ligands. However, few studies are being conducted this nascent research area. With advances field, novel carborane-based complexes will likely prepared, structurally characterized, intrinsically investigated. To expedite these efforts, we present major findings from recent studies, including π–π interactions, associations, steric effects, which have been leveraged implement a regioselective process for activating B(2,9)–, B(2,8)–, B(2,7)–H bonds para-carboranes B(4,7)–H ortho-carboranes. Future should clarify interactions potential enhancing utility complexes. Although exhibit several (such dihydrogen-bond [Bδ+–Hδ−···Hδ+–Cδ−], Bδ+–Hδ−···M+, Bδ+–Hδ−···π interactions), manner they utilized remains unclear. Supramolecular those based on chemistry, platform demonstrating applications interactions. Owing importance alkane separation, related recognition separation isomers primarily summarized. Advances certainly lead more possibilities

Язык: Английский

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Highly Robust Metal–Organic Framework for Efficiently Catalyzing Knoevenagel Condensation and the Strecker Reaction under Solvent-Free Conditions

Inorganic Chemistry, Год журнала: 2023, Номер 62(32), С. 12989 - 13000

Опубликована: Авг. 2, 2023

Metal–organic frameworks (MOFs) have been recognized as one of the most promising porous materials and offer great opportunities for rational design new catalytic solids having structural diversity functional tunability. Despite numerous inherent merits, their chemical environment instability limits practical usage demands further exploration. Herein, by employing mixed-ligand approach, we designed developed a robust 3D Co-MOF, [Co2(μ2-O)(TDC)2(L)(H2O)2]·2DMF (H2TDC = 2,5-thiophenedicarboxylic acid, L 3,3′-azobispyridine), IITKGP-50 (IITKGP stands Indian Institute Technology Kharagpur), which exhibited excellent framework robustness not only in water but also wide range aqueous pH solutions (pH 2–12). Taking advantage superior presence high-density open metal sites, was explored catalyzing two-component Knoevenagel condensation reaction three-component Strecker reactions. Moreover, to verify size selectivity IITKGP-50, smaller bulkier substrates comparison with MOF's pore cavity (8.1 × 5.6 Å2) were employed, relatively lesser conversions sterically aldehyde derivatives confirmed that cycle occurs inside cavity. The easy scalability, lower catalyst loading compared benchmark MOFs, magnificent conversion rate over substrates, recyclability without significant performance loss made heterogeneous candidate.

Язык: Английский

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Isoreticular Preparation of Tetraphenylethylene‐based Multicomponent Metallacages towards Light‐Driven Hydrogen Production

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 19, 2023

Abstract Multicomponent metallacages can integrate the functions of their different building blocks to achieve synergetic effects for advanced applications. Herein, based on metal‐coordination‐driven self‐assembly, we report preparation a series isoreticular tetraphenylethylene‐based metallacages, which are well characterized by multinuclear NMR, ESI‐TOF‐MS and single‐crystal X‐ray diffraction techniques. The suitable integration photosensitizing tetraphenylethylene units as faces Re catalytic complexes pillars into single metallacage offers high photocatalytic hydrogen production rate 1707 μmol g −1 h , is one highest values among reported metallacages. Femtosecond transient absorption DFT calculations reveal that serve platform precise organized arrangement two blocks, enabling efficient directional electron transfer highly performance. This study provides general strategy multifunctional ligands certain improve efficiency production, will guide future design towards photocatalysis.

Язык: Английский

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Self-Assembly of a Water-Soluble Pd₁₆ Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(22), С. 15301 - 15308

Опубликована: Май 24, 2024

Designing supramolecular architectures with uncommon geometries has always been a key goal in the field of metal–ligand coordination-driven self-assembly. It acquires added significance if functional building units are employed constructing such for fruitful applications. In this report, we address both these aspects by developing water-soluble Pd16L8 coordination cage 1 an unusual square orthobicupola geometry, which was used selective aerobic oxidation aryl sulfides. Self-assembly benzothiadiazole-based tetra-pyridyl donor L ditopic cis-[(tmeda)Pd(NO3)2] acceptor [tmeda = N,N,N′,N′-tetramethylethane-1,2-diamine] produced 1, and geometry determined single-crystal X-ray diffraction study. Unlike typically observed tri- or tetrafacial barrel, present assembly features distinctive structural topology is unique example molecular architecture geometry. Efficient sulfides to sulfoxides important challenge as conventional generally leads formation sulfoxide along toxic sulfone. Cage designed ligand containing benzothiadiazole moiety, demonstrates ability photogenerate reactive oxygen species (ROS) water, thus enabling it serve potential photocatalyst. The showed excellent catalytic efficiency highly conversion alkyl their corresponding sulfoxides, therefore without sulfones other byproducts, under visible light aqueous medium.

Язык: Английский

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Multicomponent, Multicavity Metallacages That Contain Different Binding Sites for Allosteric Recognition

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(23), С. 15787 - 15795

Опубликована: Май 13, 2024

The encapsulation of different guest molecules by their recognition domains proteins leads to selective binding, catalysis, and transportation. Synthetic hosts capable selectively binding guests in cavities mimic the function are highly desirable but challenging. Here, we report three ladder-shaped, triple-cavity metallacages prepared multicomponent coordination-driven self-assembly. Interestingly, porphyrin-based metallacage is heteroleptic fullerenes (C60 or C70) coronene using its cavities, allowing distinct allosteric upon addition C60 C70. Owing affinities one molecule central cavity two units side while encapsulating C70 cavity. rational design multicavity assemblies that enable will guide further advanced supramolecular constructs with tunable properties.

Язык: Английский

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Coordination cages integrated into swelling poly(ionic liquid)s for guest encapsulation and separation

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 4, 2024

Abstract Coordination cages have been widely reported to bind a variety of guests, which are useful for chemical separation. Although the use in solid state benefits recycling, flexibility, dynamicity, and metal-ligand bond reversibility solid-state poor, preventing efficient guest encapsulation. Here we report type coordination cage-integrated materials that can be swelled into gel water. The material is prepared through incorporation an anionic Fe II 4 L 6 cage as counterion cationic poly(ionic liquid) (MOC@PIL). immobilized within MOC@PILs found greatly affect swelling ability thus mechanical properties. Importantly, upon swelling, uptake water provides ideal microenvironment gels dynamically move flex leads excellent solution-level binding performances. This concept has enabled adsorbents removal pollutants from purification toluene cyclohexane. regenerated deswelling strategy along with recycling extracted guests.

Язык: Английский

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Engineering Helical Chirality in Metal-Coordinated Cyclodextrin Nanochannels

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7325 - 7335

Опубликована: Фев. 18, 2025

Helicates are a defining element of DNAs and proteins, with functions that critical to variety biological processes. Cyclodextrins promising candidates for forging multiple-stranded helicates well-defined helicity, but lack available tools has precluded the construction artificial helical nanochannels controllable geometry helicity from these widely chiral building blocks. Herein, we disclose family Ag6L2 can be readily assembled α-cyclodextrin-derived ligands through coordination between pyridinyl groups Ag+ cations. We discovered exhibit either an M or P when cations adopt tetrahedral while losing most their linearly coordinated. Both precisely controlled by simply changing number methyl at ortho positions ligands. The tetracoordinated interconnect into infinite two-dimensional coordinative network characterized hexagonal tessellation. Theoretical calculations, which reveal lower energies conformations observed in crystals compared those inverted counterparts, support experimental results.

Язык: Английский

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