Gas-phase fragmentation of 1-adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively 2H-labeled guest molecules

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F70883521%3A28110%2F17%3A63516067" target="_blank" >RIV/70883521:28110/17:63516067 - isvavai.cz</a>

Alternative codes found

RIV/70883521:28610/17:63516067

Result on the web

<a href="http://dx.doi.org/10.1002/rcm.7919" target="_blank" >http://dx.doi.org/10.1002/rcm.7919</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/rcm.7919" target="_blank" >10.1002/rcm.7919</a>

Result language

angličtina

Original language name

Gas-phase fragmentation of 1-adamantylbisimidazolium salts and their complexes with cucurbit[7]uril studied using selectively 2H-labeled guest molecules

Original language description

Rationale: Bisimidazolium salts (BIMs) represent an interesting family of ditopic ligands that are used in the construction of supramolecular systems with hosts based on cyclodextrins or cucurbit[n]urils. Understanding the fragmentation mechanism of individual BIMs and how this mechanism changes after complexation with cucurbit[n]urils can bring new insight into the intrinsic host-guest relationship, thereby allowing utilization of mass spectrometry to describe binding behavior. Methods: Selectively 2H-labeled bisimidazolium salts were prepared and fully characterized by spectroscopic methods. All MSn experiments were conducted in the positive-ion mode using an electrospray ionization (ESI) ion-trap mass spectrometer. The structures of the proposed fragments were supported by theoretical optimizations performed at the B3LYP/6-31G(d) level of density functional theory (DFT) using the Spartan&apos;14 program. Results: Using selectively deuterium-labeled isotopologues of two adamantylated bisimidazolium salts and DFT calculations, we describe the fragmentation pathways of bisimidazolium salts. The release of two important adamantane moieties, [C11H17]+ and C11H16, from M2+ was determined, although the former was strongly preferred. In contrast, when M2+ was complexed with CB7, the neutral loss of the C11H16 fragment was favored. The fragmentation pattern strongly depended on the steric hindrance of the M2+ guest against slippage of the CB7 unit over the guest molecular axle. Conclusions: The structures of two adamantane-based fragments and the mechanisms of their formation were rationalized. Two distinct geometric arrangements for the adamantane cage inside the CB7 cavity were hypothesized to explain the differences in the fragmentation patterns for guests with minimal, moderate, and high steric hindrance. This finding brings new insight into the understanding of intrinsic behavior of the adamantane-based guests inside the CB7 cavity.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10406 - Analytical chemistry

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Rapid Communications in Mass Spectrometry

ISSN

0951-4198

e-ISSN

—

Volume of the periodical

31

Issue of the periodical within the volume

18

Country of publishing house

GB - UNITED KINGDOM

Number of pages

9

Pages from-to

1510-1518

UT code for WoS article

000407391400004

EID of the result in the Scopus database

2-s2.0-85027303488