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Molecular photoswitches based on the norbornadiene--quadricylane (NBD--QC) couple have been proposed as key elements of molecular solar-thermal energy storage schemes. To characterise the intrinsic properties of such systems, reversible isomerization of a charge-tagged NBD-QC carboxylate couple is investigated in a tandem ion mobility mass spectrometer, using light to induce intramolecular [2+2] cycloaddition of NBD carboxylate to form the QC carboxylate and driving the back reaction with molecular collisions. The NBD carboxylate photoi