Unravelling the complexities of inorganic and supramolecular self-assembly in solution with electrospray and cryospray mass spectrometry.

Electrospray (ESI) and cryospray mass spectrometry (CSI-MS) are proving to be exceptionally versatile tools when used in conjunction with high resolution time-of-flight (TOF) systems to investigate the self-assembly of supramolecular architectures, inorganic coordination and organometallic compounds, labile molecules and clusters both from a structural and mechanistic point of view. In this feature article, we review very recent progress where mass spectrometry is being applied to highly labile and complex coordination and polyoxometalate (POM) cluster systems and we present some highlights from our initial electrospray and cryospray studies, which probe the self-assembly of inorganic cluster architectures. We discuss the major contributions of ESI and CSI-MS to labile and self-assembling inorganic architectures with great emphasis on future potential and ramifications for inorganic chemistry and the area of self-assembly as a whole.