Enantiopure trigonal bipyramidal coordination cages templated by in situ self-organized D2h-symmetric anions DOI Creative Commons

Shan Guo,

Wenwen Zhan, Feng‐Lei Yang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: July 4, 2024

Abstract The control of a molecule’s geometry, chirality, and physical properties has long been challenging pursuit. Our study introduces dependable method for assembling D 3 -symmetric trigonal bipyramidal coordination cages. Specifically, 2h anions, like oxalate chloranilic self-organize around metal ion to form chiral-at-metal anionic complexes, which template the formation chirality bipyramid is determined by point chiral amines used in forming ligands. Additionally, these cages exhibit selectivity included template. broadly applicable various ligand systems, enabling construction larger when are employed. Furthermore, we successfully produce enantiopure with anthracene-containing backbones using this approach, would be otherwise infeasible. These circularly polarized luminescence, modulable through reversible photo-oxygenation anthracenes.

Language: Английский

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

93

Guest‐Regulated Generation of Reactive Oxygen Species from Porphyrin‐Based Multicomponent Metallacages for Selective Photocatalysis DOI
Ke Gao, Ying Cheng, Zeyuan Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 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

Language: Английский

Citations

19

Light‐Responsive Supramolecular Liquid‐Crystalline Metallacycle for Orthogonal Multimode Photopatterning DOI Open Access

Yi‐Xiong Hu,

Xingtian Hao,

Dan Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Nov. 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.

Language: Английский

Citations

32

Supramolecular Architectures Bearing Half-Sandwich Iridium- or Rhodium-Based Carboranes: Design, Synthesis, and Applications DOI
Peng‐Fei Cui,

Xin-Ran Liu,

Guo‐Xin Jin

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(36), P. 19440 - 19457

Published: Aug. 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

Language: Английский

Citations

29

Highly Robust Metal–Organic Framework for Efficiently Catalyzing Knoevenagel Condensation and the Strecker Reaction under Solvent-Free Conditions DOI
Rupam Sahoo, Supriya Mondal,

Santanu Chand

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(32), P. 12989 - 13000

Published: Aug. 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.

Language: Английский

Citations

26

Isoreticular Preparation of Tetraphenylethylene‐based Multicomponent Metallacages towards Light‐Driven Hydrogen Production DOI
Chaoqun Mu, Lei Zhang, Guoping Li

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 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.

Language: Английский

Citations

25

Self-Assembly of a Water-Soluble Pd16 Square Bicupola Architecture and Its Use in Aerobic Oxidation in Aqueous Medium DOI
P.K. Maitra, S. Bhattacharyya, Neal Hickey

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15301 - 15308

Published: May 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.

Language: Английский

Citations

15

Multicomponent, Multicavity Metallacages That Contain Different Binding Sites for Allosteric Recognition DOI
Haifei Liu, Chenxing Guo, Luqi Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15787 - 15795

Published: May 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.

Language: Английский

Citations

13

Coordination cages integrated into swelling poly(ionic liquid)s for guest encapsulation and separation DOI Creative Commons
Xiang Zhang, Dawei Zhang, Chenyang Wei

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 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.

Language: Английский

Citations

11

Chiral Truxene‐Based Self‐Assembled Cages: Triple Interlocking and Supramolecular Chirogenesis DOI Creative Commons

Simon Séjourné,

Antoine Labrunie,

Clément Dalinot

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Jan. 29, 2024

Incorporating chiral elements in host-guest systems currently attracts much attention because of the major impact such structures may have a wide range applications, from pharmaceuticals to materials science and beyond. Moreover, development multi-responsive -functional is highly desirable since they offer numerous benefits. In this context, we describe herein construction metal-driven self-assembled cage that associates truxene-based ligand bis-ruthenium complex. The maximum separation between both facing units assembly fixed by intermetallic distance within lateral complex (8.4 Å). resulting cavity was shown encapsulate polyaromatic guest molecules, but also afford triply interlocked [2]catenane structure. formation latter occurs at high concentration, while its disassembly could be achieved addition planar achiral molecule. Interestingly molecule exhibits induced circular dichroism signature when trapped cavity, thus demonstrating ability induce supramolecular chirogenesis.

Language: Английский

Citations

10