Phase-mediated controllable intramolecular and intermolecular photocycloadditions assisted by supramolecular templates

Wang, Yishou; Sun, Li‐Ying; Wang, Yao‐Yu; Han, Ying‐Feng

doi:10.1007/s11426-022-1237-x

Cited by 6 publications

(2 citation statements)

References 38 publications

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“…56,57 Among the photochemical reactions, template-assisted photocycloaddition has played an important role in the synthesis of cyclobutane-containing compounds in recent years. 37,58–61 However, it is still challenging to control the configurations of the photoproducts in homogeneous solutions using this photochemical strategy. In homogeneous solution photoreactions, the reactant molecules generally behave chaotically, thereby creating several problems in selectivity and yield.…”

Section: Single Crystal Platforms Of Olefinic Cps For Precise Organic...mentioning

confidence: 99%

Construction of olefinic coordination polymer single crystal platforms: precise organic synthesis, in situ exploration of reaction mechanisms and beyond

Zhang,

Wang,

Braunstein

et al. 2024

Chem. Soc. Rev.

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Section: Single Crystal Platforms Of Olefinic Cps For Precise Organic...mentioning

confidence: 99%

Construction of olefinic coordination polymer single crystal platforms: precise organic synthesis, in situ exploration of reaction mechanisms and beyond

Zhang,

Wang,

Braunstein

et al. 2024

Chem. Soc. Rev.

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“…Recently, a phase-mediated controllable intramolecular and intermolecular [2 + 2] photocycloaddition was achieved using crown ether-bridged poly-NHC metallacycles [M( A41 )]BF 4 (M = Ag I , Au I ) bearing pendant methyl cinnamate moieties (Figure ). In the solution, [M( A41 )]BF 4 quantitatively underwent intramolecular [2 + 2] cycloaddition to afford photodimers [M( B41a )]BF 4 (M = Ag I , Au I ). In the solid state, two twisted molecules of [Au( A41 )]BF 4 stack together and exclusively yield intermolecular photodimer [Au 2 ( B41b )](BF 4 ) 2 in 100% conversion upon irradiation.…”

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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Stimuli‐Responsive Interconversion between Poly‐NHC‐Based Organometallic Assemblies and Their Self‐Aggregated Dimers

Jin,

Han

2024

Chin. J. Chem.

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Comprehensive SummaryPoly‐NHC‐based organometallic assemblies 3‐PF6, 3‐SbF6 and 3‐OTf were obtained and verified by NMR spectroscopy, ESI mass spectrometry and single‐crystal X‐ray diffraction analyses. Controllable structural interconversion was observed between the poly‐NHC‐based organometallic assemblies and their self‐aggregated dimers in solution affected by concentration, solvent and metal ion. 1H NMR spectra of assembly 3‐PF6 in CD3CN at different concentrations demonstrated controllable structural interconversion, and 19F NMR spectrum of assembly 3‐PF6 at high concentration further evidenced the presence of the free hexafluorophosphate anion and encapsulated hexafluorophosphate anion for its two sets of signals. In addition, single‐crystal X‐ray diffraction analysis provided clear evidence that in the solid state, two assemblies 3‐PF6 were vertically stuck, forming a self‐aggregated dimer with an encapsulated hexafluorophosphate anion. Investigating the reversible structural interconversion is beneficial for revealing the intrinsic nature on the atom level and paving the way to design the stimuli‐responsive functional system.

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Phase-mediated controllable intramolecular and intermolecular photocycloadditions assisted by supramolecular templates

Cited by 6 publications

References 38 publications

Construction of olefinic coordination polymer single crystal platforms: precise organic synthesis, in situ exploration of reaction mechanisms and beyond

Construction of olefinic coordination polymer single crystal platforms: precise organic synthesis, in situ exploration of reaction mechanisms and beyond

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

Stimuli‐Responsive Interconversion between Poly‐NHC‐Based Organometallic Assemblies and Their Self‐Aggregated Dimers

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