Desorption of crown ether–alkali metal ion complexes in liquid secondary ion mass spectrometry (LSIMS)

Giraud, Denis; Scherrens, Isabelle; Lever, Marie-Laurence; Laprévôte, Olivier; Das, Bhupesh C.

doi:10.1039/p29960000901

Cited by 8 publications

(8 citation statements)

References 34 publications

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“…Complexation Studies. Mass spectrometry has proved to be a powerful tool in the study of host−guest chemistry . Thus, the capability of FABMS to reproduce crown ether selectivity toward metal cations was reported 10b soon after the introduction of this technique.…”

Section: Resultsmentioning

confidence: 99%

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges

et al. 1999

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A redox responsive ligand incorporating the tetrathiafulvalene unit has been synthesized. The crystal structure of the free ligand (Z)-1 (C(20)H(30)O(5)S(8), triclinic P&onemacr;, Z = 2, a = 9.087(6) Å, b = 11.637(7) Å, c = 14.370(8) Å, alpha = 65.54(3) degrees, beta = 82.32(5) degrees, gamma = 84.18(6) degrees, V = 1368 Å(3)) shows the redox-active tetrathiafulvalene core to be essentially planar, which allows observation of two reversible one-electron processes upon electrochemical oxidation. The efficiency of this system in the control of the reversible complexation/expulsion sequence of a metallic cation (i.e., Ba(2+)) has been made possible thanks to a combination of (a) an unprecedented high coordination ability among tetrathiafulvalene-based macrocycles as determined by LSI mass spectrometry (log K degrees = 3.5, NBA-matrix) as well as by solution investigations ((1)H NMR and cyclic voltammetry titration studies), which remarkably converge to similar binding constant values (i.e., log K degrees = 4.2-4.3), and (b) reversible metal cation expulsion upon electrochemical oxidation to the dicationic state. A channel-like solid-state structure is observed for the Ba(2+) complex (C(20)H(30)O(5)S(8), Ba(2+)(CF(3)SO(3))(2)(2-), (H(2)O)(2), CD(3)CN, monoclinic C2/c, Z = 8, a = 45.66(1) Å, b = 8.897(5) Å, c = 23.124(8) Å, beta = 105.54(4) degrees, V = 9050 Å(3)), which results from the segregated stacking mode of the crown ether and the redox-active tetrathiafulvalene subunits, respectively.

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Section: Resultsmentioning

confidence: 99%

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges

et al. 1999

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“…The identification of the different species present in the coordinated compounds by MS requires the use of soft ionization/desorption techniques such as FAB‐MS,7a,7b,7f LSIMS6e,6f,7c,7d and ESI‐MS in the positive mode 3f,7b,7e…”

Section: Resultsmentioning

confidence: 99%

Macrocyclic 14‐Membered‐Ring Diketal Dilactams: Spectroscopic Studies and Conformational Analysis of Their Complexes with Divalent Cations

et al. 2010

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The complexation behaviour of four new 14‐membered‐ring diketal dilactam macrocycles towards some divalent cation perchlorates has been investigated. Stoichiometries and binding constants were determined by 1H NMR titration experiments. The structures of the complexes were studied by IR, NMR (1H and 13C) and electrospray mass spectrometry. 13C longitudinal relaxation time data allowed identification of the donor atoms involved in the complexation and provided information on the intramolecular mobility of the complexed ligands. Molecular modelling was also used to gain further insights into the conformational changes undergone by these molecules as a result of metal ligation. It was found that i. the macrocycles formed complexes of essentially 1:1 stoichiometry in the binding order Sr2+ ≥ Ca2+ > Mg2+ > Ba2+, ii. the coordination process caused conformational changes that resulted in cleavage of the hydrogen bonds in the ligand structure and a new orientation of the NH–CO bonds and iii. the coordination of the cations involved either all six oxygen atoms of the ligands or five of them, depending on whether the OMe groups were cis or trans, and probably two oxygen atoms from the ClO4– counter‐anion.

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“…The less-solvated ion species led to more intense ion signals (K > Na, Cs > Li) in the LSIMS spectra of 18-C-6-alkali cation complexes. 30 The observed selectivity sequence [see Figure 7(a)] was K + > Rb + > Na +~C s + > Li + corresponding to the binding free energies in a variety of solvents, but differing from gas-phase binding enthalpies (viz. Li + > Na + > K + > Rb + > Cs + ).…”

Section: Selectivity Of Ce 1 and Ce 2 Towards Metal Cationsmentioning

confidence: 99%

Scope and Limitation of Matrix-Assisted Laser Desorption/Ionization Fourier Transform Mass Spectrometry for Testing the Complexing Behavior of Two Crown Ethers Derived from D-Hexopyranosides

Calba¹,

Müller²,

Schmitt-Dubessy

et al. 2002

Eur J Mass Spectrom (Chichester)

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The complexing abilities of two macrocycles, namely a 18-C-6 crown ether (CE 1) and a 20-C-6 crown ether (CE 2) towards one organic guest [protonated phenethylamine (PEAH +)], were investigated with help of matrix-assisted laser desorption/ionization (MALDI) Fourier transform mass spectrometry. A qualitative correlation between the complexation behavior of CE 1 in solution and in the gas phase of the spectrometer could be established. We concluded from these results that a fine control of laser irradiance and the use of a suitable sample protocol allowed the preservation of weak molecular interactions throughout the MALDI process. The observed positive ions can be considered as being already present in the deposited solid solution and merely liberated by the laser pulse.

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Desorption of crown ether–alkali metal ion complexes in liquid secondary ion mass spectrometry (LSIMS)

Cited by 8 publications

References 34 publications

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges

Macrocyclic 14‐Membered‐Ring Diketal Dilactams: Spectroscopic Studies and Conformational Analysis of Their Complexes with Divalent Cations

Scope and Limitation of Matrix-Assisted Laser Desorption/Ionization Fourier Transform Mass Spectrometry for Testing the Complexing Behavior of Two Crown Ethers Derived from D-Hexopyranosides

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