Understanding the fundamental reactivity of polymetallic complexes is challenging due to the complexity of their structures with many possible bond breaking and forming processes. Here, we apply ion mobility mass spectrometry coupled with density functional theory to investigate the disassembly mechanisms and energetics of a family of heterometallic rings and rotaxanes with the general formula [NH 2 RR'][Cr 7 MF 8 (O 2 C t Bu) 16 ] with
The implementation of a quantum computer requires both to protect information from environmental noise and to implement quantum operations efficiently. Achieving this by a fully fault-tolerant platform, in which quantum...
Following electrospray ionization, it is common for analytes to enter the gas phase accompanied by a charge-carrying ion, and in most cases, this addition is required to enable detection in the mass spectrometer. These small charge carriers may not be influential in solution but can markedly tune the analyte properties in the gas phase. Therefore, measuring their relative influence on the target molecule can assist our understanding of the structure and stability of the analyte. As the formed adducts are usually distinguishable by their mass, differences in the behavior of the analyte resulting from these added species (e.g., structure, stability, and conformational dynamics) can be easily extracted. Here, we use ion mobility mass spectrometry, supported by density functional theory, to investigate how charge carriers (H + , Na + , K + , and Cs + ) as well as water influence the disassembly, stability, and conformational landscape of the homometallic ring [Cr 8 F 8 (O 2 C t Bu) 16 ] and the heterometallic rotaxanes [NH 2 RR′][Cr 7 MF 8 (O 2 C t Bu) 16 ], where
Following electrospray ionization (ESI), it is common for analytes to enter the gas phase accompanied by an additional small ion or molecule. Although these may not be influential in solution, they often determine the charge of the entire complex and can markedly tune their properties in the gas phase. Therefore, measuring their relative influence can be used to assist our understanding of the structure and stability of the target molecule. Because these adducts are usually distinguishable by their mass, differences in the behaviour of the analyte resulting from these added species can be extracted readily. Here, we use ion mobility mass spectrometry (IM-MS), supported by density functional theory (DFT), to investigate how different charge carriers (H+, Na+, K+, Cs+) as well as water influence the disassembly, stability, and conformational landscape of the homometallic ring [Cr8F8(O2CtBu)16] and different heterometallic rotaxanes [NH2RR’][Cr7MF8(O2CtBu)16], where M = Mn, Fe, Co, Ni, Cu, Zn, and Cd. The results yield new insights on their disassembly mechanisms and support previously reported trends in cavity size and transition metal properties, demonstrating the potential of adduct ion studies for characterising metallosupramolecular complexes in general.
Understanding the fundamental reactivity of polymetallic complexes is challenging due to the complexity of their structures with many possible bond breaking and forming processes. Here we apply ion mobility mass spectrometry (IM-MS) coupled with density functional theory (DFT) to investigate the disassembly mechanisms and energetics of a family of heterometallic rings and rotaxanes with the general formula [NH2RR’][Cr7MF8(O2CtBu)16] with M = MnII, FeII, CoII, NiII, CuII, ZnII, CdII. Our results show that their stability can be tuned both by altering the d-metal composition in the macrocycle and by the end groups of the secondary ammonium cation [NH2RR’]+. Ion mobility probes the conformational landscape of the disassembly process from intact complex to structurally distinct isobaric fragments, providing unique insights to how a given divalent metal tunes the structural dynamics.
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