Affiliation:
1. Institute of Chemistry, Faculty of Natural Science II, Martin-Luther-University Halle-Wittenberg, Halle, Germany
Abstract
A comparative mass spectrometric investigation using electrospray ionisation (ESI) and liquid injection field desorption/ionisation (LIFDI) techniques is reported for the highly luminescent and cationic copper cluster [(PCP)[Formula: see text]Cu[Formula: see text]][Formula: see text] (1[Formula: see text], PCP = [1,3-(Ph[Formula: see text]P)[Formula: see text]C[Formula: see text]H[Formula: see text]][Formula: see text]). Depending on the available counter ion X[Formula: see text], ion pairs consisting of the original or a modified cluster cation and the weakly coordinating counter ion can be detected by LIFDI-high-resolution-mass spectrometry in addition to the cluster cation. Notably, only large counter ions with an extremely low tendency for metal coordination give rise to the observation of ion pairs, whereas smaller ions such as BF[Formula: see text] do not show peaks corresponding to ion pairs in their mass spectra. In principle, two pathways were identified for the formation of positively charged ion pairs: (i) association of a generated Cu[Formula: see text] ion to the neutral ion pair [(PCP)[Formula: see text]Cu[Formula: see text]]X (1+X, X[Formula: see text] = BAr[Formula: see text], BAr[Formula: see text]) and (ii) abstraction of an electron from the neutral ion pair [(PCP)[Formula: see text]Cu[Formula: see text]]X (1+X), leading to the oxidised ion pair [1+X][Formula: see text] (X[Formula: see text] = Al(OR[Formula: see text])[Formula: see text]).
Funder
Deutsche Forschungsgemeinschaft
Subject
Spectroscopy,Atomic and Molecular Physics, and Optics,General Medicine
Cited by
4 articles.
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