Abstract
Structural determination of inorganic clusters relies heavily on mass spectrometry because of, in most cases, their poor responsivities toward nuclear magnetic resonance, ultraviolet/visible, and infrared analyses. Nevertheless, mass spectrometry analysis of oligosulfurs (Sn), which are unique clusters with copious allotropic forms, usually displays their fragment peaks. Here we report that a polyaromatic capsule acts as a supramolecular matrix for the mass determination of the neutral sulfur clusters. Upon encapsulation, molecular ion peaks derived from the host–guest complexes including cyclic S6 and S8 clusters are exclusively detected by common electrospray ionization time-of-flight mass spectrometry analysis. Furthermore, mass spectrometry analysis of a cyclic S12 cluster, which is in situ prepared from two S6 clusters within the matrix upon light irradiation, is achieved by the same way. The present matrix can remarkably stabilize the otherwise labile S6 and S12 clusters in the polyaromatic shell not only under mass spectrometry conditions but also in an ambient solution state.
Highlights
Structural determination of inorganic clusters relies heavily on mass spectrometry because of, in most cases, their poor responsivities toward nuclear magnetic resonance, ultraviolet/ visible, and infrared analyses
We firstly carried out the quantitative encapsulation and mass determination of cyclooctasulfur (S8) using capsular matrix 1 in water
After removal of suspended free S8 by filtration, the 1:2 host–guest structure was confirmed by nuclear magnetic resonance (NMR), UV-visible, and X-ray crystallographic analyses
Summary
Structural determination of inorganic clusters relies heavily on mass spectrometry because of, in most cases, their poor responsivities toward nuclear magnetic resonance, ultraviolet/ visible, and infrared analyses. We report that a polyaromatic capsule acts as a supramolecular matrix for the mass determination of the neutral sulfur clusters. Molecular ion peaks derived from the host–guest complexes including cyclic S6 and S8 clusters are exclusively detected by common electrospray ionization time-of-flight mass spectrometry analysis. There are many reports on the successful stabilization and observation of highly reactive organic and organometallic compounds within supramolecular cages and capsules[8,9,10,11,12,13,14,15,16,17,18] Those of labile inorganic clusters are limited to white phosphorus (Fig. 1c)[19] and yellow arsenic[20, 21]. We accomplish selective preparation of a cyclic S12 cluster from two S6 clusters within the matrix upon light irradiation, as revealed by subsequent MS analysis of the host–guest complex
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