A palladium–carbon-connected organometallic framework and its catalytic application

Dong, Ying; Jv, Jing-Jing; Wu, Xiaowei; Kan, Jing‐Lan; Lin, Tai-Chia; Dong, Yu‐Bin

doi:10.1039/c9cc07829k

Cited by 10 publications

(7 citation statements)

References 22 publications

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“…The CNDipp CC Ar and CN-1-(2- i Pr)-Naph arylisocyanide ligands of interest in this work are depicted in Figure . The former were prepared according to modified literature procedures. ,, Like their CNDippAr counterparts, all CNDipp CC Ar ligands can be prepared from the same readily accessible synthetic intermediate, N -formyl-4-iodo-2,6-diisopropylaniline. Sonogashira coupling of this reagent with phenylacetylene, 1-naphthylacetylene, 9-phenanthrenylacetylene, 4-methoxyphenylacetylene, or 4-cyanophenylacetylene, followed by dehydration of the resulting formamide with OPCl 3 , yields the isocyanide ligands CNDipp CC Ph, CNDipp CC -1-Naph, CNDipp CC -9-Phen, CNDipp CC Ph OMe , and CNDipp CC Ph CN , respectively, in moderate yield (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

et al. 2020

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Homoleptic tungsten(0) arylisocyanides possess photophysical and photochemical properties that rival those of archetypal ruthenium(II) and iridium(III) polypyridine complexes. Previous studies established that extending the π-system of 2,6diisopropylphenylisocyanide (CNDipp) by coupling aryl substituents para to the isocyanide functionality results in W(CNDippAr) 6 oligoarylisocyanide complexes with greatly enhanced metal-to-ligand charge transfer (MLCT) excited-state properties relative to those of W(CNDipp) 6 . Extending electronic modifications to delineate additional design principles for this class of photosensitizers, herein we report a series of W(CNAr) 6 compounds with naphthalene-based fused-ring (CN-1-(2-i Pr)-Naph) and CNDipp-based alkynyl-bridged (CNDipp CC Ar) arylisocyanide ligands. Systematic variation of the secondary aromatic system in the CNDipp CC Ar platform provides a straightforward method to modulate the photophysical properties of W(CNDipp CC Ar) 6 complexes, allowing access to an extended range of absorption/luminescence profiles and highly reducing excited states, while maintaining the high molar absorptivity MLCT absorption bands, high photoluminescence quantum yields, and long excited-state lifetimes of previous W(CNAr) 6 complexes. Notably, W(CN-1-(2-i Pr)-Naph) 6 exhibits the longest excited-state lifetime of all W(CNAr) 6 complexes explored thus far, highlighting the potential benefits of utilizing fused-ring arylisocyanide ligands in the construction of tungsten(0) photoreductants.

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Section: Resultsmentioning

confidence: 99%

Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

et al. 2020

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“…34−44 Accordingly, despite their charge neutrality, the dual bonding interactions provided by isocyanides lead to strong metal−ligand linkages that can be harnessed for reticular network formation. 24,25,45 It was shown that [CNAr Mes2 ] 2 could provide a series of robust, singlecrystalline frameworks featuring Cu(I)-based single-metal structural nodes (i.e., Cu-ISO CNs 1−3; ISO CN = isocyanide coordination network; Scheme 1). 24 In certain cases, these frameworks retain their thermal integrity up to ca.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Recently, we reported an approach to overcoming this challenge by using the rigid and linear ditopic m -terphenyl diisocyanide, [CNAr Mes2 ] 2 , as a linker group (Ar Mes2 = 2,6-(2,4,6-Me 3 C 6 H 2 ) 2 C 6 H 3 ; Scheme ). , Isocyanide ligands have long been recognized for their ability to function as both good σ-donors and strong π-acids, − which are properties that are particularly advantageous for the stabilization of electron-rich metal centers. − Accordingly, despite their charge neutrality, the dual bonding interactions provided by isocyanides lead to strong metal–ligand linkages that can be harnessed for reticular network formation. ,, It was shown that [CNAr Mes2 ] 2 could provide a series of robust, single-crystalline frameworks featuring Cu(I)-based single-metal structural nodes (i.e., Cu- ISO CNs 1–3; ISO CN = isocyanide coordination network; Scheme ). In certain cases, these frameworks retain their thermal integrity up to ca.…”

Section: Introductionmentioning

confidence: 99%

Aqueous Stability and Ligand Substitution of a Layered Cu(I)/Isocyanide-Based Organometallic Network Material with a Well-Defined Channel Structure

et al. 2020

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Isocyanide coordination networks (ISOCNs), which consist of multitopic isocyanide linker groups and transition-metal-based secondary building units (SBUs), are a promising class of organometallic framework materials for the inclusion of low-valent metal centers as primary structural components. Previously, it was demonstrated that the ditopic m-terphenyl isocyanide ligand, [CNArMes2]2 (ArMes2 = 2,6-(2,4,6-Me3C6H2)2C6H3), could provide single-metal node frameworks based on Cu(I) and Ni(0) centers. However, the relatively short linker length in [CNArMes2]2 precluded the formation of networks with significant porosity. Here, it is shown that expansion of the [CNArMes2]2 scaffold with a central phenylene spacer allows for the formation of a robust Cu(I)-based framework with a distinct and solvent accessible channel structure. This new framework, denoted Cu-ISOCN-4, is prepared as single-crystalline samples from a solvothermal reaction between [Cu(NCMe)4]PF6 and expanded linker 1,4-(CNArMes2)2C6H4. Crystallographic characterization of Cu-ISOCN-4 revealed mononuclear [Cu(THF)(CNR)3]+ structural nodes. The expanded diisocyanide linker results in fourfold interpenetrated (6,3) internal morphology. However, interpenetration in Cu-ISOCN-4 results in discrete layer domains, each of which possesses well-defined 29 × 19 Å channels along the crystallographic b axis. Thermogravimetric analysis on Cu-ISOCN-4 revealed THF solvent loss from the channels between 100–200 °C and dissociation of the Cu-coordinated THF ligand at 290 °C. The overall integrity of the network remains intact up to 400 °C, thereby signifying the robust nature of materials produced from metal-isocyanide M-C linkages. Aqueous stability studies revealed that Cu-ISOCN-4 remains chemically resistant to exposure to liquid water for several days. In addition, ligand exchange studies in both THF and aqueous solution demonstrate that the Cu-coordinated THF group in Cu-ISOCN-4 can be readily substituted with pyridine. This ligand exchange process occurs via single-crystal-to-single-crystal transformations and can also be readily monitored by infrared spectroscopy.

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“…In 2019, Dong and co-workers reported a 2D Pd II LVMOF formed by the solvothermal reaction between a tritopic isocyanide linker and PdI 2 . [58] This LVMOF was applied as a heterogeneous catalyst for Suzuki-Miyaura coupling to produce substituted biphenyls. Significantly, in comparison to molecular Pd-isocyanide catalysts, the LVMOF required lower reaction temperatures, shorter [51] B) synthesis and crystal structure of Cu-ISO CN-4 highlighting 3-connected Cu I node and extended structure of a single 2D sheet; [52] C) synthesis and crystal structure of Ni-ISO CN-2 with view of extended structure and tetrahedral Ni 0 nodes.…”

Section: Methodsmentioning

confidence: 99%

Metal–Organic Frameworks with Low‐Valent Metal Nodes

et al. 2022

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Metal-organic frameworks (MOFs) are crystalline, 2-and 3-dimensional coordination polymers formed by bonding interactions between metals and multitopic organic ligands. These are typically formed using hard Lewis basic organic ligands with high oxidation state metal ions. The use of low-valent metals as structural elements in MOFs is far less common, despite the widespread use of such metals for catalysis, luminescence, and other applications. This Minireview focuses on recent advances in the field of low-valent MOFs and offers a perspective on the future development of these materials.

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A palladium–carbon-connected organometallic framework and its catalytic application

Abstract: A Pd–C-bond-connected organometallic framework and its catalytic activity for the Suzuki–Miyaura cross-coupling reaction were reported.

Cited by 10 publications

References 22 publications

Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

Aqueous Stability and Ligand Substitution of a Layered Cu(I)/Isocyanide-Based Organometallic Network Material with a Well-Defined Channel Structure

Metal–Organic Frameworks with Low‐Valent Metal Nodes

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A palladium–carbon-connected organometallic framework and its catalytic application

Abstract: A Pd–C-bond-connected organometallic framework and its catalytic activity for the Suzuki–Miyaura cross-coupling reaction were reported.

Cited by 10 publications

References 22 publications

Third-Generation W(CNAr)6 Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

Third-Generation W(CNAr)6 Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

Aqueous Stability and Ligand Substitution of a Layered Cu(I)/Isocyanide-Based Organometallic Network Material with a Well-Defined Channel Structure

Metal–Organic Frameworks with Low‐Valent Metal Nodes

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Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)

Third-Generation W(CNAr)₆ Photoreductants (CNAr = Fused-Ring and Alkynyl-Bridged Arylisocyanides)