Controlled Formation of Fused Metal Chalcogenide Nanoclusters Using Soft Landing of Gaseous Fragment Ions.

The complete ligation of nanoclusters significantly reduces their chemical reactivity, catalytic activity, and charge transfer properties. Therefore, in applications, nanoclusters are activated through partial ligand removal to take advantage of their full potential. However, the precise control of ligand removal in the condensed phase is challenging. In this study, we examine the reactivity of well-defined activated nanoclusters on surfaces prepared through controlled ligand removal in the gas phase. To accomplish this, we utilized a specially designed ion soft-landing instrument equipped with a collision cell to prepare mass-selected fragment ions, which were then deposited onto self-assembled monolayer (SAM) surfaces. Specifically, we generated fragment ions by selectively removing one or two ligands from a series of atomically precise ligated metal sulfide clusters, Co5MS8(L1)6+ (M = Co, Mn, Fe, or Ni, L1 = PEt3). Removal of one ligand from Co5MS8(L1)6+ (M = Co, Mn, Ni) generates Co5MS8(L1)5+ species, which undergo selective dimerization on SAMs. Meanwhile, Co5FeS8(L1)5+ is unreactive and remains intact when it is deposited onto a SAM surface. In contrast, fragments formed by the removal of two ligands, Co5MS8(L1)4+, undergo several nonselective reactions and generate larger fused clusters. We found that the reactivity of the Co5MS8(L1)5+ fragment ions is correlated with the gas phase stability of the corresponding precursor ion toward ligand loss. Specifically, the relatively unstable precursor ion, Co5FeS8(L1)6+, generates the least reactive fragment. Meanwhile, the more stable precursor ions generate more reactive Co5MS8(L1)5+ fragments that dimerize on surfaces. This observation was also confirmed by co-deposition of fragment ions with two different ligands, Co5MS8(L1)5+ and Co5MS8(L2)5+ (L1 = PEt3 and L2 = PEt2Ph), where fragments generated from more stable precursor ions tend to dimerize and generate dimers with mixed ligands. This study unveils the previously unrecognized potential of fragment ions in generating compounds that are difficult to synthesize using conventional methods. Additionally, it provides a mechanistic understanding of the observed reactivity. Mass-selected deposition of well-defined fragment ions emerges as a powerful approach for designing materials by precisely activating and depositing undercoordinated ligated nanoclusters onto surfaces.

A Sulfur-Controlled Approach to the Synthesis of Linerixibat.

Establishing the two stereocenters in the benzothiazepine ring of linerixibat (GSK2330672) has been a long-standing problem at GSK. Our solution rests on an episulfonium-controlled Ritter reaction followed by a sulfoxide-directed reduction. A rationale for both steps is based on a mixture of literature precedent and computational experiments. Transition state modeling suggests the sulfoxide-directed reduction proceeds through electronic repulsion between the lone pair of electrons on sulfur and the incoming borohydride anion.

Soft landing of polyatomic anions onto three-dimensional semiconductive and conductive substrates.

Soft landing of well-characterized polyoxometalate anions, PW12O40 3- (WPOM) and PMo12O40 3- (MoPOM), was carried out to explore the distribution of anions in the semiconducting 10 and 6 µm-long vertically aligned TiO2 nanotubes as well as 300 µm-long conductive vertically aligned carbon nanotubes (VACNTs). The distribution of soft-landed anions on the surfaces and their penetration into the nanotubes were studied using energy dispersive X-ray spectroscopy (EDX) and scanning electron microscopy (SEM). We observe that soft landed anions generate microaggregates on the TiO2 nanotubes and only reside in the top 1.5 µm of the nanotube height. Meanwhile, soft landed anions are uniformly distributed on top of VACNTs and penetrate into the top 40 µm of the sample. We propose that both the aggregation and limited penetration of POM anions into TiO2 nanotubes is attributed to the lower conductivity of this substrate as compared to VACNTs. This study provides first insights into the controlled modification of three dimensional (3D) semiconductive and conductive interfaces using soft landing of mass-selected polyatomic ions, which is of interest to the rational design of 3D interfaces for electronics and energy applications.

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

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.

Multiplexing of Electrospray Ionization Sources Using Orthogonal Injection into an Electrodynamic Ion Funnel.

In this contribution, we report an efficient approach to multiplex electrospray ionization (ESI) sources for applications in analytical and preparative mass spectrometry. This is achieved using up to four orthogonal injection inlets implemented on the opposite sides of an electrodynamic ion funnel interface. We demonstrate that both the total ion current transmitted through the mass spectrometer and the signal-to-noise ratio increase by 3.8-fold using four inlets compared to one inlet. The performance of the new multiplexing approach was examined using different classes of analytes covering a broad range of mass and ionic charge. A deposition rate of >10 µg of mass-selected ions per day may be achieved by using the multiplexed sources coupled to preparative mass spectrometry. The almost proportional increase in the ion current with the number of ESI inlets observed experimentally is confirmed using gas flow and ion trajectory simulations. The simulations demonstrate a pronounced effect of gas dynamics on the ion trajectories in the ion funnel, indicating that the efficiency of multiplexing strongly depends on gas velocity field. The study presented herein opens up exciting opportunities for the development of bright ion sources, which will advance both analytical and preparative mass spectrometry applications.

Designing New Metal Chalcogenide Nanoclusters through Atom-by-Atom Substitution.

Atom-by-atom substitution is a promising strategy for designing new cluster-based materials, which has been used to generate new gold- and silver-containing clusters. Here, the first study focused on atom-by-atom substitution of Fe and Ni to the core of a well-defined cobalt sulfide superatom [Co6 S8 L6 ]+ ligated with triethylphosphine (L = PEt3 ) to produce [Co5 MS8 L6 ]+ (M = Fe, Ni) is reported. Electrospray ionization mass spectrometry confirms the substitution of 1-6 Fe atoms with the single Fe-substituted cluster being the dominant species. The Fe-substituted clusters oxidize in solution to generate dicationic species. In contrast, only a single Ni-substituted cluster is observed, which remains stable as a singly charged species. Collision-induced dissociation experiments indicate the reduced stability of the [Co5 FeS8 L6 ]+ toward ligand loss in comparison with the unsubstituted and Ni-substituted counterparts. Density functional theory calculations provide insights into the effect of metal atom substitution on the stability and electronic structures of the clusters. The results indicate that Fe and Ni have a different impact on the electronic structure, optical, and magnetic properties, as well as ligand-core interaction of [Co6 S8 L6 ]. This study extends the atom-by-atom substitution strategy to the metal chalcogenide superatoms providing a direct path toward designing novel atomically precise core-tailored superatoms.