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[M+CuCl+H] 2+  ions were generated using electrospray ionization (ESI); where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester (1 and 2, respectively). The ions were subjected to CID-MS/MS analysis. It was found that their gas phase decomposition lead to the formation of rare di-cations [M] 2+ , namely [1] 2+  and [2] 2+  ions. The formation of [1] 2+  ion from [3+H+CuCl] 2+  ion in the second fragmentation, where 3 is ethyl ester of 3,5-bis(2,2-bipyridin-4-ylethynyl)benzoic acid, was also observed since in the first fragmentation step the loss of ethylene molecule from [3+H+CuCl] 2+  ion took place. To the best of our knowledge, it is the first time that [M] 2+  ions formation from respective metal complexes has been reported. It is also unusual that formation of [M] 2+  ions is not accompanied by formation of [M] +∙  ions. Furthermore, as expected, theoretical calculation and electron ionization mass spectra show that 1 and 2 are not especially prone to form [M] 2+  ions. Thus formation of [M] 2+  ions under CID conditions is very surprising.

open chemistry

Unexpected formation of [M] 2+  from [M+CuCl+H] 2+  ions under CID conditions, where M is a molecule of 3,5-bis(2,2’-bipyridin-4-ylethynyl)benzoic acid or its methyl ester