Can you eliminate the DMF from the reaction medium or change the reagent for once to confirm if this is derived from the DMF complex formation? It is very likely an adduct formed by DMF additive...You indicated the step-by-step evaluation you followed. After which synthesis reaction step (meaning which new additives are in the reaction pot) may induce this adduct?
By the way, what is your sample matrix ? Do you use sodium or potassium and organic acid matrix additives to induce ionization but also suppress non-specific adduct variants...?
Lastly, for your target do you observe protonated or other main adducts simultaneously with +75 or only M+75 is the pseudomolecular parent ion?