Formation of diclofenac molecular ions as the effect of Cu(2+)-π interaction under electrospray ionization mass spectrometry conditions.

Solutions containing diclofenac (M) and a copper salt [CuCl2, Cu(ClO4)2, Cu(NO3)2, CuSO4) were analysed by electrospray ionisation mass spectrometry (ESI-MS). Because of the cation-pi interactions in diclofenac-Cu(II) complexes, the diclofenac molecular ion M+* at m/z 295 was formed. It was found that the solvent composition (methanol versus water/methanol) and counter ion strongly affect the M+* ion formation. Formation pathways of ion M+* are discussed.