Supramolecular Template-Assisted Catalytic [2+2] Photocycloaddition in Homogeneous Solution

Wang, Fang; Bai, Sha; Zhu, Qing-Wen; Wei, Zi-Hang; Han, Ying‐Feng

doi:10.31635/ccschem.022.202201919

Cited by 13 publications

(11 citation statements)

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“…Recently, supramolecular assemblies have been regarded as promising media to enhance the efficiency and topochemistry of photoreactions. 5,6 By taking advantage of versatile supramolecular interactions, photoactive units can be preorganized in a specific geometry toward the incoming photoproduct. As a result, a range of cucurbiturils, cyclodextrins, and hydrogen-bonding templates have been successfully utilized to improve the selectivity of photochemical [4 + 4] cycloadditions of monosubstituted anthracene derivatives ( AD s), such as 2- and 9- AD s. 7–13 In contrast to this, the supramolecular control of disubstituted AD s, especially 2,6- and 2,7- AD s, not only suffered from the generation of a mixture of syn - and anti - dAD photodimers (Fig.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular-controlled regioselective photochemical [4 + 4] cycloaddition within Cp*Rh-based metallarectangles

Bai

Wang

et al. 2022

Dalton Trans.

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Section: Introductionmentioning

confidence: 99%

Supramolecular-controlled regioselective photochemical [4 + 4] cycloaddition within Cp*Rh-based metallarectangles

Bai

Wang

et al. 2022

Dalton Trans.

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“…Thus, poly-NHC assemblies and their related photoproducts have become available for applications beyond supramolecular synthesis. For example, cyclobutane derivatives L′ (Figures b and b) can be modified to new functionalized M–NHC complexes with limitations imposed by synthetic complexity. , Cyclobutanes lined with pyridyl groups are intriguing potential building blocks for metallosupramolecular architectures and materials.…”

Section: Properties and Applications Of The Productsmentioning

confidence: 99%

“…During the process, template D1 shows a strong tendency to transform to D2 after photocycloaddition, thus rendering the reaction stoichiometric. To overcome this drawback, we designed a relatively rigid dinuclear Au I –NHC complex D3 featuring two sterically hindered benzimidazolones (Figure a) . Under optimized conditions, mono- and bidentate olefin substrates were tolerated in the catalytic [2 + 2] photocycloaddition in solution catalyzed by D3 .…”

Section: Supramolecular Control Of Photoreactions Based On the M–nhc ...mentioning

confidence: 99%

Metal-N-Heterocyclic Carbene Chemistry Directed toward Metallosupramolecular Synthesis and Beyond

Bai

Han

2023

Acc. Chem. Res.

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Conspectus As versatile, modular, and strongly coordinating moieties in organometallic compounds, N-heterocyclic carbenes (NHCs) have led to numerous breakthroughs in transition-metal catalysis, main group chemistry, and organocatalysis. In contrast, the chemistry of NHC-based metallosupramolecular assemblies, in which discrete individual components are held together via metal (M)–CNHC bonds, has been underdeveloped. Integrating NHCs into supramolecular assemblies would endow them with some unforeseen functions. However, one of the most critical challenges is seeking an appropriate combination of the rigid CNHC–M–CNHC units with the resulting topologies and applications. Toward this goal, for the last decade we have focused on the development of M–NHC directed toward metallosupramolecular synthesis. This Account aims to summarize our contributions to the application of M–NHC chemistry toward supramolecular synthesis from structural design to postassembly modification (PAM) and their functional applications since integrating NHCs into supramolecular assemblies has garnered much attention among organometallic, photochemical, and supramolecular researchers. While presenting representative examples of NHC-based architectures, we try to illustrate the purposes and concepts behind the systems developed to aid the rational approach to the design and fabrication of complex assemblies and M–NHC-templated photochemical reactions. We present synthetic approaches for new architectures by the rational design of starting NHC precursors, including the poly-NHC-based mechanically interlocked metallacages and the heteroleptic architectures based on electronic complementary and self-sorting mechanisms. The structural regulation of poly-NHC-based architectures with increasing topological complexity is elaborated on by selective combinations of tetraphenylethylene (TPE) units, NHC backbones, and N-wingtip substituents in a controllable manner. Subsequently, we move to elucidating an M–NHC-templated PAM approach that leads to functional organic cages featuring polyimidazolium/triazolium groups of different shapes and sizes that are difficult to access using alternative organic approaches. These organic cages possess well-defined cavities, and their in situ-generated NHC sites are ideal platforms for stabilizing metal nanoparticles (MNPs) within their cavities for improved catalytic performance. Finally, we demonstrate how to design supramolecular M–NHC templates to synthesize cyclobutane derivatives in homogeneous solutions in a catalytic fashion. Selected examples of M–NHC template-dependent structural transformations and photoreactions are discussed. Their applications in molecular recognition, aggregation-induced emission (AIE), cell imaging, anticancer activity, radical chemistry, and stimuli-responsive materials are also described. Taken together, M–NHC-templated approaches have proven to be powerful methods for constructing diverse architectures with functional applications. The development of this methodology is still in its i...

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“…1,2 Organometallic supramolecular assemblies obtained by metal-carbene-directed self-assembly from N-heterocyclic carbene (NHC) ligands have been dramatically developed in stimulus-responsive organometallic materials, catalysis, and photochemical reactions. [3][4][5][6][7][8] This strategy utilizes the directional advantages of metal-carbene bonding to adequately control the design of various NHC-based supramolecular architectures. In the library of reported NHC complexes, a series of macrocycles, cages and other interlocked organometallic complexes have been constructed from coinage metals (Ag I , Au I , and Cu I ) and well-designed NHC ligands, binding in a fixed linear geometry.…”

Section: Introductionmentioning

confidence: 99%

Hierarchical self-assembly of a radical naphthalenediimide-based N-heterocyclic carbene-Au(i) macrocycle

Wang

Zhu

et al. 2023

Inorg. Chem. Front.

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Supramolecular Template-Assisted Catalytic [2+2] Photocycloaddition in Homogeneous Solution

Cited by 13 publications

References 0 publications

Supramolecular-controlled regioselective photochemical [4 + 4] cycloaddition within Cp*Rh-based metallarectangles

Supramolecular-controlled regioselective photochemical [4 + 4] cycloaddition within Cp*Rh-based metallarectangles

Metal-N-Heterocyclic Carbene Chemistry Directed toward Metallosupramolecular Synthesis and Beyond

Hierarchical self-assembly of a radical naphthalenediimide-based N-heterocyclic carbene-Au(i) macrocycle

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