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

Kód výsledku v 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>

Nalezeny alternativní kódy

RIV/70883521:28610/17:63516067

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10406 - Analytical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

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

Rok uplatnění

2017

Kód důvěrnosti údajů

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

Název periodika

Rapid Communications in Mass Spectrometry

ISSN

0951-4198

e-ISSN

—

Svazek periodika

31

Číslo periodika v rámci svazku

18

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

1510-1518

Kód UT WoS článku

000407391400004

EID výsledku v databázi Scopus

2-s2.0-85027303488