Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

Liu, Die; Chen, Mingzhao; Li, Yiming; Shen, Yixian; Huang, Jian; Yang, Xiao‐Yu; Jiang, Zhilong; Li, Xiaopeng; Newkome, George R.; Wang, Pingshan

doi:10.1002/anie.201809819

Cited by 39 publications

(26 citation statements)

References 59 publications

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“…Figure was reproduced from Ref. [96] with permission of the copyright holders. Self-assembly of supramolecular 3D wheel.…”

Section: Discussionmentioning

confidence: 99%

“…Recently, Wang and co-workers disclosed a giant 3D supramolecular double-and tripledecker hexagon structure by using covalent link to vertically coordinate two or three layers of plane spoked wheels together based on <tpy-M 2+-tpy> connectivity (Fig. 13) [96]. The ligand was synthesized through several Suzuki cross-coupling reaction.…”

Section: Iteration On 3d Levelmentioning

confidence: 99%

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Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Wei

Shi

et al. 2019

Coordination Chemistry Reviews

194

121

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As an NNN-tridentate ligand, the 2,2':6',2"-terpyridine plays an important role in coordination chemistry. With three coordination sites and low LUMO, terpyridine and its derivatives are one of the typical Pincer ligand and/or non-innocent ligands in transition metal catalysis. Interesting catalytic reactivities have been obtained with these tpy-metal complexes targeting some challenging transformations, such as CC bond formation and hydrofunctionalization. On the other hand, terpyridine ligands can form "closed-shell" octahedral complexes, which provide a linear and stable linkage in supramolecular chemistry. Numerous supramolecular architectures have been achieved using modified terpyridine ligands including Sierpiński triangles, hexagonal gasket and supramolecular rosettes. This review presents a summary of recent progress regarding transition metal-terpyridine complexes with the focus on their applications in catalysis and supramolecular structure construction. Facile synthesis of terpyridine derivatives is also described. We hope this article can serve to provide some general perspectives of the terpyridine ligand and their applications in coordination chemistry.

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“…Figure was reproduced from Ref. [96] with permission of the copyright holders. Self-assembly of supramolecular 3D wheel.…”

Section: Discussionmentioning

confidence: 99%

Section: Iteration On 3d Levelmentioning

confidence: 99%

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Wei

Shi

et al. 2019

Coordination Chemistry Reviews

194

121

View full text Add to dashboard Cite

show abstract

“…Among the numerous reports of organic ligands, 2,2′:6′,2″-terpyridine (tpy) derivatives, which can coordinate with diverse transition metal ions to form a linearly-coordinated pseudo-octahedral <tpy-M 2+ -tpy> connection and ultimate supramolecular architectures, has gained extensive attention in the field of supramolecular self-assembly. [18][19][20] Up to the present, a variety of discrete metallo-supramolecular architectures based on tpy groups have been extensively reported, including spoked wheels, [21] pentagram, [22] hexagons, [23] cube, [24] and Sierpiński triangles. [25] With increasing size and complexity for expected structure, the self-assembly using multi-terpyridinyl monomers as ligand still faces more challenges.…”

Section: Doi: 101002/marc202000095mentioning

confidence: 99%

From Dimeric to Octameric Metallo‐Supramolecular Macrocycles Based on Sterically Congested Ligand–assisted Self‐Assembly with Zn(II), Cd(II), and Fe(II)

Guan

Zhang

et al. 2020

Macromol. Rapid Commun.

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Two sterically congested 2,2′:6′,2″‐terpyridine‐based ligands LA and LB, composed of asymmetrically contiguous terpyridine units, are designed and synthesized for metallo‐supramolecular architectures. The significant advantage of this design is that the terpyridines in these ligands have different chemical environments and show a selective coordination ability with each other. For ditopic ligand LA, the self‐assembly with Zn(II), Cd(II), and Fe(II) gave the rhombic dimers, which have the same sets of terpyridine signals as ligand LA. The self‐assembly behavior of tritopic ligand LB with Cd(II) and Zn(II) are observed for discrete tetramers under thermodynamic control, whereas ligand LB and Fe(II) are assembled to generate a mixture of tetramer, hexamer, and octamer, which are successfully isolated using regular chromatographic separation. Moreover, the sterically congested ligands and metal ions formed stable intermediates to drive the formation of discrete structures, which is also proved by mixing LB and Cd(II) with a precise stoichiometric ratio of 1:1. These supramolecular complexes are thoroughly characterized by NMR spectroscopy, electrospray ionization‐mass spectrometry, and 2D traveling‐wave ion mobility‐mass spectrometry. This conceptually new design of sterically congested ligands provides a novel strategy for precisely controlled supramolecular complexes with diverse architectures.

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“…The development of supramolecular assemblies is one of the most promising strategies for encapsulating catalytically relevant elements in a confined space. This allows for their performance to be regulated by rational design of the assembly host rather than merely relying on inner-sphere ligands, reminiscent of enzymes with regard to catalytic acceleration by proximity effects in pocket 10–20 . While success has been achieved using these systems in the context of homogeneous catalysis, to meet the challenges associated with product purification and catalyst reusability, tethering these supramolecular catalysts on insoluble carriers would allow for an increase in operational ability 21 .…”

Section: Introductionmentioning

confidence: 99%

Bio-inspired creation of heterogeneous reaction vessels via polymerization of supramolecular ion pair

et al. 2019

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Precise control of the outer-sphere environment around the active sites of heterogeneous catalysts to modulate the catalytic outcomes has long been a challenge. Here, we demonstrate how this can be fulfilled by encapsulating catalytic components into supramolecular capsules, used as building blocks for materials synthesis, whereby the microenvironment of each active site is tuned by the assembled wall. Specifically, using a cationic template equipped with a polymerizable functionality, anionic ligands can be encapsulated by ion pair-directed supramolecular assembly, followed by construction into porous frameworks. The hydrophilic ionic wall enables reactions to be achieved in water that usually requires organic solvents and also facilitates the enrichment of the substrate into the hydrophobic pocket, leading to superior catalytic performances as demonstrated by the industrially relevant hydroformylation. Remarkably, the formation of the supramolecular assembly and catalyst encapsulation further engenders reaction selectivity, which reaches an even greater extent after construction of the porous framework.

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Vertical Assembly of Giant Double‐ and Triple‐Decker Spoked Wheel Supramolecular Structures

Cited by 39 publications

References 59 publications

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

Terpyridine-metal complexes: Applications in catalysis and supramolecular chemistry

From Dimeric to Octameric Metallo‐Supramolecular Macrocycles Based on Sterically Congested Ligand–assisted Self‐Assembly with Zn(II), Cd(II), and Fe(II)

Bio-inspired creation of heterogeneous reaction vessels via polymerization of supramolecular ion pair

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