Gas phase ion chemistry of titanium–oxofullerene with ligated solvents

Roy, Jayoti; Chakraborty, Papri; Paramasivam, Ganesan; Natarajan, Ganapati; Pradeep, Thalappil

doi:10.1039/d1cp04716g

Cited by 3 publications

(3 citation statements)

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“…Theoretical mass calculations revealed that the crystal consisted of these clusters and a certain number of water and methanol molecules that were derived from the solvent system. Similar solvent-associated peaks were also observed in other metal nanoclusters. − The broad isotopic distribution in the mass spectrum can be attributed to two factors: (1) molybdenum (Mo) has seven naturally stable isotopes, resulting in a wide isotopic distribution along with the contributions of naturally abundant isotopes from various atoms i.e., Na, O, S, C, P, and H present in the nanoclusters, and (2) the small mass differences (Δ m ≈ 9–11) between individual nanoclusters in their trianionic state. Additionally, these nanoclusters ionize by getting attached to one or two solvent molecules (H 2 O = 18 and MeOH = 32), which further contributes to the broad distribution of a specific charge state observed.…”

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confidence: 75%

Structure and Electrocatalytic Performance of Cocrystallized Ternary Molybdenum Oxosulfide Clusters for Efficient Water Splitting

Mondal,

Jana,

Roy

et al. 2023

ACS Materials Lett.

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Polyoxometalates (POMs) belong to a class of metal oxyanion clusters that hold enormous promise for a wide range of catalytic reactions, due to their structural diversity and the presence of redox-active metal centers and heteroatomic sites within the framework. In this study, we successfully determined the structures of the first cocrystallized ternary molybdenum oxo-sulfide clusters: Mo12NaO54P8C48H40, Mo12NaS2O52P8C48H40, and Mo12NaS6O48P8C48H40, which are abbreviated as Mo12, Mo12@S2, and Mo12@S6, respectively. Together, they are referred to as Mo12-TC. These clusters exhibit nearly identical exterior structures, making them indistinguishable, leading to their cocrystallization in a single unit cell with 50%, 25%, and 25% occupancy for Mo12, Mo12@S2, and Mo12@S6, respectively, and could not be separated easily. To confirm their molecular formulae and occupancy within a crystal, we conducted single-crystal X-ray diffraction (SCXRD) and high-resolution electrospray ionization–mass spectrometry (ESI-MS) studies. The clusters exhibit a dumbbell-like shape, with each terminal of the dumbbell comprising a hexagonal Mo6 basal plane shielded by multiple oxo, and oxosulfide moieties for Mo12 and Mo12@S2/Mo12@S6 clusters, respectively. Additionally, the clusters are protected by a ligand shell consisting of vertically aligned phenylphosphonic acid (PPA). Mo12-TC demonstrates promising activity for electrochemical hydrogen and oxygen evolution reactions (HER and OER). Mo12-TC exhibits overpotentials of 0.262 and 0.413 V vs RHE to reach HER current densities (in H2SO4) of 10 and 100 mA cm–2, respectively, and overpotentials of 0.45 and 0.787 V vs RHE to reach OER current densities (in KOH) of 10 and 100 mA cm–2, respectively, stable up to 5000 cycles. Density functional theory (DFT) calculations further elucidate their electrocatalytic potential, revealing the presence of active sites within these molecular frameworks.

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confidence: 75%

Structure and Electrocatalytic Performance of Cocrystallized Ternary Molybdenum Oxosulfide Clusters for Efficient Water Splitting

Mondal,

Jana,

Roy

et al. 2023

ACS Materials Lett.

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“…As a result, mass spectrometry (MS) has been extensively used to study structures and reactivity of cluster ions and supramolecular chemistry of interest, leading to the development of cluster-based materials. [9][10][11][12][13] For example, gas phase dissociation studies of mass-selected clusters through collision induced dissociation (CID) enables the characterization of structures, binding energies, and stability of clusters towards fragmentation. [14][15][16][17][18][19][20] By combining gas phase studies with electronic structure calculations, the intrinsic geometric and electronic structures of clusters may be determined which cannot be obtained using conventional characterization methods.…”

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confidence: 99%

“…Mass spectrometric characterization of molecular clusters circumvents some of these challenges. As a result, mass spectrometry (MS) has been extensively used to study structures and reactivity of cluster ions and supramolecular chemistry of interest, leading to the development of cluster-based materials 9 – 13 . For example, gas-phase dissociation studies of mass-selected clusters through collision-induced dissociation (CID) enable the characterization of structures, binding energies, and stability of clusters towards fragmentation 14 – 20 .…”

Section: Introductionmentioning

confidence: 99%

Gas-phase fragmentation of single heteroatom-incorporated Co5MS8(PEt3)6+ (M = Mn, Fe, Co, Ni) nanoclusters

et al. 2022

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Functionalization of metal-chalcogenide clusters by either replacing core atoms or by tuning the ligand is a powerful technique to tailor their properties. Central to this approach is understanding the competition between the strength of the metal-ligand and metal-metal interactions. Here, using collision-induced dissociation of atomically precise metal sulfide nanoclusters, Co5MS8L6+ (L = PEt3, M = Mn, Fe, Co, Ni) and Co5-xFexS8L6+ (x = 1–3), we study the effect of a heteroatom incorporation on the core-ligand interactions and relative stability towards fragmentation. Sequential ligand loss is the dominant dissociation pathway that competes with ligand sulfide (LS) loss. Because the ligands are attached to metal atoms, LS loss is an unusual dissociation pathway, indicating significant rearrangement of the core prior to fragmentation. Both experiments and theoretical calculations indicate the reduced stability of Co5MnS8L6+ and Co5FeS8L6+ towards the first ligand loss in comparison with their Co6S8L6+ and Co5NiS8L6+ counterparts and provide insights into the core-ligand interaction.

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Gas-phase fragmentation of single atom incorporated Co5MS8(PEt3)6+ (M=Mn, Fe, Co, Ni) nanoclusters

Ranjbar¹,

Deepika²,

Jena

et al. 2022

Preprint

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Functionalization of metal-chalcogenide clusters by either replacing one or more of the core metal atoms or by choosing the ligand is a powerful technique to tailor their properties and synthesize cluster assembled materials. Central to this approach is to understand the competition between the strength of the metal-ligand and metal-metal interactions within the cluster. We use collision-induced dissociation (CID) of two series of atomically precise metal sulfide nanoclusters including Co5MS8L6+ (L=PEt3, M= Mn, Fe, Co, Ni) and Co5-xFexS8L6+ (x=1-3) to understand the effect of a heteroatom incorporation on the core-ligand interactions and relative stability towards fragmentation. We observe sequential ligand loss as the dominant dissociation pathway for all the clusters, which occurs in competition with the loss of ligand sulfide (LS). Because all the ligands are attached to metal atoms in the precursor cluster cations, LS loss is an unusual dissociation pathway, indicative of a rearrangement of the cluster prior to fragmentation. Collision energy-resolved CID combined with theoretical calculations reveals the reduced stability of Co5MnS8L6+ and Co5FeS8L6+ cations towards the loss of the first ligand in comparison with their Co6S8L6+ and Co5NiS8L6+ counterparts. Moreover, we observe that the relative stability of clusters towards ligand loss as well as the competition between ligand and LS losses are strongly dependent on the composition of the clusters. Theoretical studies also confirm that the first ligand always prefers to detach from the doped-metal atom site to form Co5MS8L5+ cations. This study provides new insight into modulation of the core-ligand interaction of the atomically precise metal chalcogenide clusters suggesting paths to generate reactive species to promote inter-cluster reactions.

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Gas phase ion chemistry of titanium–oxofullerene with ligated solvents

Abstract: Gas phase fragmentation events of fullerene-like titanium oxo-cluster anions were investigated in detail. The fragmentation channel of the ions was comparable to the fragmentation of C60 ions with systematic C2 losses which is a consequence of topological similarity.

Cited by 3 publications

References 54 publications

Structure and Electrocatalytic Performance of Cocrystallized Ternary Molybdenum Oxosulfide Clusters for Efficient Water Splitting

Structure and Electrocatalytic Performance of Cocrystallized Ternary Molybdenum Oxosulfide Clusters for Efficient Water Splitting

Gas-phase fragmentation of single heteroatom-incorporated Co5MS8(PEt3)6+ (M = Mn, Fe, Co, Ni) nanoclusters

Gas-phase fragmentation of single atom incorporated Co5MS8(PEt3)6+ (M=Mn, Fe, Co, Ni) nanoclusters

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