TY - JOUR
T1 - Adduct Ions as Diagnostic Probes of Metallosupramolecular Complexes Using Ion Mobility Mass Spectrometry
AU - Geue, Niklas
AU - Bennett, Tom S.
AU - Ramakers, Lennart A.I.
AU - Timco, Grigore A.
AU - McInnes, Eric J.L.
AU - Burton, Neil A.
AU - Armentrout, P. B.
AU - Winpenny, Richard E.P.
AU - Barran, Perdita E.
N1 - Funding Information:
N.G. is grateful for funding through the President’s Doctoral Scholar Award by The University of Manchester. We acknowledge the support of EPSRC through the strategic equipment award EP/T019328/1, the European Research Council for funding the MS SPIDOC H2020-FETOPEN-1-2016-2017-801406, and Waters Corporation for their continued support of mass spectrometry research within the Michael Barber Centre for Collaborative Mass Spectrometry. R.E.P.W. thanks the EPSRC for an Established Career Fellowship (EP/R011079/1) and the European Research Council for an Advanced Grant (ERC-2017-ADG-786734). P.B.A. thanks the National Science Foundation, Grant CHE-1954142, for support. The authors would like to acknowledge the assistance given by Research IT and the use of the Computational Shared Facility at The University of Manchester. The authors also thank the staff in the MS and Separation Science Facility in the Faculty of Science and Engineering, The University of Manchester, for their assistance.
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/2/13
Y1 - 2023/2/13
N2 - 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 [Cr8F8(O2CtBu)16] and the heterometallic rotaxanes [NH2RR′][Cr7MF8(O2CtBu)16], where M = MnII, FeII, CoII, NiII, CuII, ZnII, and CdII. 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 characterizing metallosupramolecular complexes in general.
AB - 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 [Cr8F8(O2CtBu)16] and the heterometallic rotaxanes [NH2RR′][Cr7MF8(O2CtBu)16], where M = MnII, FeII, CoII, NiII, CuII, ZnII, and CdII. 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 characterizing metallosupramolecular complexes in general.
UR - http://www.scopus.com/inward/record.url?scp=85147215145&partnerID=8YFLogxK
UR - https://www.mendeley.com/catalogue/232c2c75-6c6a-3db9-8b5f-3aa4168a3e56/
U2 - 10.1021/acs.inorgchem.2c03698
DO - 10.1021/acs.inorgchem.2c03698
M3 - Article
C2 - 36716284
AN - SCOPUS:85147215145
SN - 0020-1669
VL - 62
SP - 2672
EP - 2679
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 6
ER -