Isolation of Homo‐/Mixed‐Valence Ag12, Ag29, and Ag8Clusters Stabilized by Cyclic Alkyl(amino) Carbene‐Anchored Monoanionic Phosphorus Ligand

Nag, Ekta; Battuluri, Sridhar; Mondal, Kartik Chandra; Roy, Sudipta

doi:10.1002/chem.202202324

Cited by 6 publications

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“…Therefore, the convergence of computational and experimental methodologies holds great promise for accelerating the discovery of new cage systems. , Particularly noteworthy is the application of rapid screening techniques of organic cages, thereby offering a consistent methodology to facilitate the development of materials with precisely tailored characteristics, , as well as the use of time-dependent DFT approaches to obtain detailed information about the electronic structure of metal clusters inside cages. , Here, we provide a detailed computational analysis of the recently described iminopyrrole cages, focusing on their intracavity dynamics, coordination plasticity, and other important properties, for which computational techniques can provide data complementary to the experimental data. Apart from the already mentioned plasticity of the system, we pay particular attention to the properties of potential mixed-valence Ag clusters, as this topic has recently attracted significant attention in the context of luminescence, fluorescence, chemical reactivity, , and other applications …”

Section: Introductionmentioning

confidence: 99%

“… 37 , 38 Here, we provide a detailed computational analysis of the recently described iminopyrrole cages, focusing on their intracavity dynamics, coordination plasticity, and other important properties, for which computational techniques can provide data complementary to the experimental data. Apart from the already mentioned plasticity of the system, we pay particular attention to the properties of potential mixed-valence Ag clusters, as this topic has recently attracted significant attention in the context of luminescence, 39 fluorescence, 40 chemical reactivity, 41 , 42 and other applications. 43 …”

Section: Introductionmentioning

confidence: 99%

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Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters

Trzaskowski,

Martínez,

Sarwa

et al. 2024

J. Phys. Chem. A

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Recently, pyrrole cages have been synthesized that encapsulate ion pairs and silver(I) clusters to form intricate supramolecular capsules. We report here a computational analysis of these structures using density functional theory combined with a semiempirical tight-binding approach. We find that for neutral pyrrole cages, the Gibbs free energies of formation provide reliable predictions for the ratio of bound ions. For charged pyrrole cages, we find strong argentophilic interactions between Ag ions on the basis of the calculated bond indices and molecular orbitals. For the cage with the Ag 4 cluster, we find two minimum-geometry conformations that differ by only 6.5 kcal/mol, with an energy barrier <1 kcal/mol, suggesting a very flexible structure as indicated by molecular dynamics. The predicted energies of formation of [Ag n ⊂1] n-3+ (n = 1−5) cryptands provide low energy barriers of formation of 5−20 kcal/mol for all cases, which is consistent with the experimental data. Furthermore, we also examined the structural variability of mixed-valence silver clusters to test whether additional geometrical conformations inside the organic cage are thermodynamically accessible. In this context, we show that the time-dependent density functional theory UV−vis spectra may potentially serve as a diagnostic probe to characterize mixed-valence and geometrical configurations of silver clusters encapsulated into cryptands.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters

Trzaskowski,

Martínez,

Sarwa

et al. 2024

J. Phys. Chem. A

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Monoanionic Phosphorus‐Supported Air Stable Cu(I)₈, Ag(I)₇, and Ag(I)₅ Nanoclusters Exhibiting TADF: A Novel Photocatalyst for Stereoselective Carbene Transfer Reactions

Nag,

Patra,

Francis

et al. 2023

Advanced Optical Materials

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Applications of structurally well‐defined coinage‐metal nanoclusters (NCs) as optoelectronic materials and homogeneous catalysts have been restricted due to their inherent lower stability. Herein, the syntheses, structural characterizations, and photoluminescence properties of three novel air‐stable coinage‐metal(I) NCs‐supported by carbene‐anchored monoanionic phosphorus (cAAC=P−) with molecular formulae [(Cy‐cAACP)4(Cu)4(CuCl)4] (4), [(Cy‐cAACP)4(Ag)4(AgOTf)3] (5), and [(Cy‐cAACP)4(Ag)5]NTf2 (6) (cAAC = cyclic alkyl(amino) carbene; Tf = CF3SO2) exhibiting thermally activated delayed fluorescence (TADF) are reported. Apart from attractive metallophilic interactions [M─M; M ═ Cu, Ag], the enhanced kinetic and thermodynamic stability of 4–6 can be attributed to the excellent π‐accepting ability of cAAC=P− surrounding the metallic cores. cAAC=P− anion is generated either in situ by anion‐induced cleavage of P−Sb/B bonds of corresponding stibanyl/boryl phosphaalkenes in the presence of coinage‐metal(I)‐Cl/OTf/NTf2 salts or by directly introducing alkali‐metal phosphinidenide. The TADF properties of 4–6 are established by smaller energy gaps between the lowest singlet excited state and triplet excited state. In solid‐state, the delayed fluorescence lifetimes of 4–6 are found to be in the microsecond range with absolute photoluminescence quantum yields up to 20%. The redox‐active Cu(I)8 NC 4 is successfully exploited as an efficient photo‐catalyst for the selective carbene transfer reaction at ambient conditions, affording cyclopropanated indoles/styrenes with excellent yields and diastereoselectivity.

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Coordination Chemistry of Bis‐Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Di‐Phosphorus (P₂): An Efficient Route to Donor Base‐Stabilized Elusive Di‐Phosphorus‐Monoxide(P₂O)‐Gold Complex

Francis,

Nag,

Roy

2023

Chemistry An Asian Journal

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The stability and reactivity studies of heavier di‐atomic group‐15 congeners of alkynes, e. g., the di‐phosphorus (P≡P) compounds have been the topic of huge interest because of their contrasting transient properties and lower stability compared to those of the stable molecular di‐nitrogen (N≡N). Herein, we depict the reactivity studies of the bis‐cAAC‐stabilized di‐phosphorus (P2) having an inversely polarized phosphaalkene nature featuring the C=P double bonds with Au(I)Cl. Both the mono‐, and the di‐aurated phosphaalkenes with the formulae [(Me2‐cAAC=P)2(AuCl)] (2), and [(Me2‐cAAC=P)2(AuCl)2] (3), respectively have been isolated in the solid state. Moreover, for the first time, we have been able to isolate the cAAC‐stabilized tetra‐aurated elusive di‐phosphorus‐monoxide (P2O) with the formula [(Cy‐cAAC=P)−O−(P=cAAC−Cy)(AuCl)4] (5) in presence of oxygen. Complexes 2–3, 5 have been structurally characterized by single crystal X‐ray diffraction, and further studied by NMR spectroscopy. Our findings reveal significant elongation of the CcAAC−P bonds in 2–3, 5, and the presence of aurophilic interaction in 5. Quantum chemical calculations, including density functional theory (DFT), and energy decomposition analysis coupled with natural orbitals for chemical valence (EDA‐NOCV) have been performed to study the electron densities distribution and nature of bonding in 2–3, 5.

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Isolation of Homo‐/Mixed‐Valence Ag₁₂, Ag₂₉, and Ag₈Clusters Stabilized by Cyclic Alkyl(amino) Carbene‐Anchored Monoanionic Phosphorus Ligand

Cited by 6 publications

References 60 publications

Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters

Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters

Monoanionic Phosphorus‐Supported Air Stable Cu(I)₈, Ag(I)₇, and Ag(I)₅ Nanoclusters Exhibiting TADF: A Novel Photocatalyst for Stereoselective Carbene Transfer Reactions

Coordination Chemistry of Bis‐Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Di‐Phosphorus (P₂): An Efficient Route to Donor Base‐Stabilized Elusive Di‐Phosphorus‐Monoxide(P₂O)‐Gold Complex

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Isolation of Homo‐/Mixed‐Valence Ag12, Ag29, and Ag8Clusters Stabilized by Cyclic Alkyl(amino) Carbene‐Anchored Monoanionic Phosphorus Ligand

Cited by 6 publications

References 60 publications

Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters

Argentophilic Interactions, Flexibility, and Dynamics of Pyrrole Cages Encapsulating Silver(I) Clusters

Monoanionic Phosphorus‐Supported Air Stable Cu(I)8, Ag(I)7, and Ag(I)5 Nanoclusters Exhibiting TADF: A Novel Photocatalyst for Stereoselective Carbene Transfer Reactions

Coordination Chemistry of Bis‐Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Di‐Phosphorus (P2): An Efficient Route to Donor Base‐Stabilized Elusive Di‐Phosphorus‐Monoxide(P2O)‐Gold Complex

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Isolation of Homo‐/Mixed‐Valence Ag₁₂, Ag₂₉, and Ag₈Clusters Stabilized by Cyclic Alkyl(amino) Carbene‐Anchored Monoanionic Phosphorus Ligand

Monoanionic Phosphorus‐Supported Air Stable Cu(I)₈, Ag(I)₇, and Ag(I)₅ Nanoclusters Exhibiting TADF: A Novel Photocatalyst for Stereoselective Carbene Transfer Reactions

Coordination Chemistry of Bis‐Cyclic Alkyl(Amino) Carbene (cAAC)‐Supported Di‐Phosphorus (P₂): An Efficient Route to Donor Base‐Stabilized Elusive Di‐Phosphorus‐Monoxide(P₂O)‐Gold Complex