Dataset Information

From Small Metal Clusters to Molecular Nanoarchitectures with a Core-Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co₃₈As₁₂(CO)₅₀]⁴.

ABSTRACT: The cluster [Co₃₈As₁₂(CO)₅₀]^4- was obtained by pyrolysis of [Co₆As(CO)₁₆]^-. The metal cage features a closed-packed core inside a Co/As shell that progressively deforms from a cubic face-centered symmetry. The redox and acid-base reactivities were determined by cyclic voltammetry and spectrophotometric titrations. The calculated electron density revealed the shell-constrained distribution of the atomic charges, induced by the presence of arsenic.

SUBMITTER: Della Pergola R

PROVIDER: S-EPMC9937531 | biostudies-literature | 2022 Jul

REPOSITORIES: biostudies-literature

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From Small Metal Clusters to Molecular Nanoarchitectures with a Core-Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co38As12(CO)50]4.

Della Pergola Roberto R Garlaschelli Luigi L Macchi Piero P Facchinetti Irene I Ruffo Riccardo R Racioppi Stefano S Sironi Angelo A

Inorganic chemistry 20220622 26

The cluster [Co38As12(CO)50]4- was obtained by pyrolysis of [Co6As(CO)16]-. The metal cage features a closed-packed core inside a Co/As shell that progressively deforms from a cubic face-centered symmetry. The redox and acid-base reactivities were determined by cyclic voltammetry and spectrophotometric titrations. The calculated electron density revealed the shell-constrained distribution of the atomic charges, induced ...[more]

PMID: 35731613

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Project description:The demand for new ionic liquid (IL)-based systems to selectively sequester carbon dioxide from gas mixtures has prompted the development of individual components involving the tailored design of IL themselves or solid-supported materials that provide excellent gas permeability of the overall material as well as the ability to incorporate large amounts of ionic liquid. In this work, novel IL-encapsulated microparticles comprising a cross-linked copolymer shell of β-myrcene and styrene and a hydrophilic core of the ionic liquid 1-ethyl-3-methylimidazolium dicyanamide ([EMIM][DCA]) are proposed as viable materials for CO2 capture. Water-in-oil (w/o) emulsion polymerization of different mass ratios of β-myrcene to styrene (i.e. 100/0, 70/30, 50/50, 0/100) yielded IL-encapsulated microparticles, where the encapsulation efficiency of [EMIM][DCA] was dependent on the copolymer shell composition. Thermal analysis using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) revealed that both thermal stability and glass transition temperatures depend on the mass ratio of β-myrcene to styrene. Images from scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to observe the microparticle shell morphology as well as measure the particle size perimeter. Particle sizes were found to be between 5 and 44 μm. CO2 sorption experiments were conducted gravimetrically using TGA instrumentation. Interestingly, a trade-off between CO2 absorption capacity and ionic liquid encapsulation was observed. While increasing the β-myrcene content within the microparticle shell increases the amount of encapsulated [EMIM][DCA], the observed CO2 absorption capacity did not increase as expected due to reduced porosity compared to microparticles with higher styrene content in the microparticle shell. [EMIM][DCA] microcapsules with a 50/50 weight ratio of β-myrcene/styrene showed the best synergistic effect between spherical particle diameter (32.2 μm), pore size (0.75 μm), and high CO2 sorption capacity of ∼0.5 mmol CO2/g sample within a short absorption period of 20 min. Therefore, core-shell microcapsules composed of β-myrcene and styrene are envisioned as a promising material for CO2 sequestration applications.

Project description:The salt [K(18-crown-6)]2[Ru(CN)2(CO)3] ([K(18-crown-6)]2[1]) was generated by the reaction of Ru(C2H4)(CO)4 with [K(18-crown-6)]CN. An initial thermal reaction gives [Ru(CN)(CO)4]-, which, upon ultraviolet (UV) irradiation, reacts with a second equiv of CN-. Protonation of [1]2- gave [HRu(CN)2(CO)3]- ([H1]-), which was isolated as a single isomer with mutually trans cyanide ligands. The complex cis,cis,cis-[Ru(pdt)(CN)2(CO)2]2- ([2]2-) was prepared by the UV-induced reaction of [1]2- with propanedithiol (pdtH2). The corresponding iron complex cis,cis,cis-[Fe(pdt)(CN)2(CO)2]2- ([3]2-) was prepared similarly. The pdt complexes [2]2- and [3]2- were treated with Fe(benzylideneacetone)(CO)3 to give, respectively, [RuFe (μ-pdt)(CN)2(CO)4]2- ([5]2-) and [Fe2(μ-pdt)(CN)2(CO)4]2- ([4]2-). The pathway from [3]2- to Fe2 complex [4]2- implicates intermetallic migration of CN-. In contrast, the formation of [5]2- leaves the Ru(CN)2(CO) center intact, as confirmed by X-ray crystallography. The structure of [5]2- features a "rotated" square-pyramidal Fe(CO)2(μ-CO) site. NMR measurements indicate that the octahedral Ru site is stereochemically rigid, whereas the Fe site dynamically undergoes turnstile rotation. 57Fe Mössbauer spectral parameters are very similar for rotated [5]2- and unrotated Fe2 complex [4]2-, indicating the insensitivity of that technique to both the geometry and the oxidation state of the Fe site. According to cyclic voltammetry, [5]2- oxidizes at E1/2 ∼ -0.8 V vs Fc+/0. Electron paramagnetic resonance (EPR) measurements show that 1e- oxidation of [5]2- gives an S = 1/2 rhombic species, consistent with the formulation Ru(II)Fe(I), related to the Hox state of the [FeFe] hydrogenases. Density functional theory (DFT) studies reproduce the structure, 1H NMR shifts, and infrared (IR) spectra observed for [5]2-. Related homometallic complexes with both cyanides on a single metal are predicted to not adopt rotated structures. These data suggest that [5]2- is best described as Ru(II)Fe(0). This conclusion raises the possibility that for some reduced states of the [FeFe]-hydrogenases, the [2Fe]H site may be better described as Fe(II)Fe(0) than Fe(I)Fe(I).

Dataset Information

From Small Metal Clusters to Molecular Nanoarchitectures with a Core-Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co₃₈As₁₂(CO)₅₀]⁴.

Publications

From Small Metal Clusters to Molecular Nanoarchitectures with a Core-Shell Structure: The Synthesis, Redox Fingerprint, Theoretical Analysis, and Solid-State Structure of [Co<sub>38</sub>As<sub>12</sub>(CO)<sub>50</sub>]<sup>4</sup>.

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