Designing New Metal Chalcogenide Nanoclusters through Atom‐by‐Atom Substitution

Abstract

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 [Co6S8L6]+ ligated with triethylphosphine (L = PEt3) to produce [Co5MS8L6]+ (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 [Co5FeS8L6]+ 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 [Co6S8L6]. 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.

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

“…Jonas Warneke and Carsten Jenne. Na­[V 6 O 7 (OCH 3 ) 12 ] and [Co 6 S 8 (PEt 3 ) 6 ]Cl were synthesized according to reported procedures. , Substance P was dissolved in a 9:1 (v/v) methanol/H 2 O solution to a concentration of 100 μM. Ubiquitin was dissolved in CH 3 OH/H 2 O/CH 3 COOH = 49.5/49.5/1 to a concentration of 20 μM.…”

The emergence of mass spectrometry for characterizing nanomaterials. Atomically precise nanoclusters and beyond

“…[104][105][106][107][108] High-resolution mass spectrometry was also applied to monitor the atom-by-atom substitution of Fe and Ni to the core of a welldefined ligated cobalt nanocluster. 109 Alloying metallic kernel from monometallic to tetrametallic was also demonstrated and the monodispersity of each alloyed nanocluster was characterized by electrospray ionization mass spectrometry analysis. 98,110 By recording mass spectra as a function of time, the evolution of the composition of a reacting mixture can even be monitored, which allows a better comprehension of the formation process, especially for alloyed nanoclusters.…”

Developing Dawson-Type Polyoxometalates Used as Highly Efficient Catalysts for Lignocellulose Transformation

“…The investigation of this interaction might provide new insights into the design of active POMs in catalysis or materials. Furthermore, POMs served as one of the most ideal species for fabricating new complexes through “atom-by-atom” substituent in a well-controlled way, which had proven superiority in precise/accurate molecular construction. − To the best of our knowledge, there is no deep understanding of Dawson H 6 V 2 Mo 18 with a transition metal as a central atom. Therefore, in the current work, experimental study and density functional theory (DFT) had been performed to clarify the mechanism for the increase in the oxidation–reduction and decrease in the acidity of H 6 V 2 Mo 18 caused by the modification of the electronic state of Mo and O atoms due to vanadium insertion.…”