Detecting the Subtle Photo-Responsive Conformational Bistability of Monomeric Azobenzene Functionalized Keggin Polyoxometalates by Using Ion-Mobility Mass Spectrometry

Accurately characterizing the conformational variation of novel molecular assemblies is important but often ignored due to limited characterization methods. Herein, we reported the use of ion-mobility mass spectrometry (IMS/MS) to investigate the conformational changes of four azobenzene covalently functionalized Keggin hybrids (azo-Keggins, compounds 1–4). The as-prepared azo-Keggins showed the general molecular formula of [C(16)H(36)N](4)[SiW(11)O(40)(Si(CH(2))(3)NH–CO(CH(2))(n)O–C(6)H(4)N=NC(6)H(4)–R)(2)] (R = H, n = 0 (1); R = NO(2), n = 0 (2); R = H, n = 5 (3); R = H, n = 10 (4)). The resultant azo-Keggins maintained stable monomeric states in the gas phase with intact molecular structures. Furthermore, the subtle photo-responsive trans-cis conformational variations of azo-Keggins were clearly revealed by the molecular shape-related collision cross-section value difference ranging from 2.44 Å(2) to 6.91 Å(2). The longer the alkyl chains linkers were, the larger the conformational variation was. Moreover, for compounds 1 and 2, higher stability in trans-conformation can be observed, while for compounds 3 and 4, bistability can be achieved for both of them.