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Title: Diffusion of a Highly-Charged Supramolecular Assembly: Direct Observation of Ion-Association in Water

Abstract

Understanding the solution behavior of supramolecular assemblies is essential for a full understanding of the formation and chemistry of synthetic host-guest systems. While the interaction between host and guest molecules is generally the focus of mechanistic studies of host-guest complexes, the interaction of the host-guest complex with other species in solution remains largely unknown, although in principle accessible by diffusion studies. Several NMR techniques are available to monitor diffusion and have recently been reviewed. Pulsed gradient spin-echo (PGSE) NMR methods have attracted increasing interest, since they allow diffusion coefficients to be measured with high accuracy; they have been successfully used with observation of {sup 7}Li and {sup 31}P nuclei as well as with {sup 1}H NMR. We report here the direct measurement of diffusion coefficients to observe ion-association interactions by counter cations with a highly-charged supramolecular assembly. Raymond and coworkers have described the design and chemistry of a class of metal-ligand supramolecular assemblies over the past decade. The [Ga{sub 4}L{sub 6}]{sup 12-} (L = 1,5-bis(2,3-dihydroxybenzamido)naphthalene) (1) (Figure 1) assembly has garnered the most attention, with the exploration of the dynamics and mechanism of guest exchange as well as the ability of 1 to achieve either stoichiometric or catalytic reactions insidemore » its interior cavity. Recent studies have revealed the importance of counter cations in solution on the chemistry of 1. During the mechanistic study of the C-H bond activation of aldehydes by [Cp*Ir(PMe{sub 3})(olefin){sup +} {contained_in} 1]{sup 11-} a stepwise guest dissociation mechanism with an ion-paired intermediate was proposed. Similarly, in the mechanism for the hydrolysis of iminium cations generated from the 3-aza Cope rearrangement of enammonium cations in 1, the presence of an exterior ion association was part of the kinetic model. To further substantiate the indirect kinetic evidence for such ion-paired species, we sought to explore the solution behavior of 1 by studying the diffusion of 1 with varying alkali and tetraalkyl ammonium cations. For large molecules in solution, such as synthetic supramolecular assemblies, the diffusion behavior of host and guest molecules can provide valuable information on host-guest interaction. One characteristic feature of a stable host-guest complex is that the host and guest molecules diffuse at the same rate in solution; this has been observed in a number of supramolecular systems. In order to confirm that this system was suitable for study by diffusion NMR spectroscopy, a PGSE-DOSY spectrum was acquired of [NEt{sub 4} {contained_in} 1]{sup 11-} (Figure 2), which shows that the host and guest molecules diffuse at the same rate. Quantitative analysis of the data, from monitoring the integral of host and guest resonances as a function of applied gradient strength, gave identical diffusion coefficients, confirming that the host and guest molecules diffuse together.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
Chemical Sciences Division
OSTI Identifier:
928951
Report Number(s):
LBNL-240E
Journal ID: ISSN 0020-1669; INOCAJ; TRN: US200811%%440
DOE Contract Number:  
DE-AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 47; Related Information: Journal Publication Date: 2008; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
37; ACCURACY; ALDEHYDES; CATIONS; CHEMISTRY; DESIGN; DIFFUSION; DISSOCIATION; EXPLORATION; HYDROLYSIS; KINETICS; MONITORING; MONITORS; NUCLEI; SPECTROSCOPY; SPIN ECHO; WATER; Highly-Charged Supramolecular Assembly

Citation Formats

University of California, Berkeley, Lawrence Berkeley National Laboratory, Raymond, Kenneth, Pluth, Michael D, Tiedemann, Bryan E.F., van Halbeek, Herman, Nunlist, Rudi, and Raymond, Kenneth N. Diffusion of a Highly-Charged Supramolecular Assembly: Direct Observation of Ion-Association in Water. United States: N. p., 2007. Web.
University of California, Berkeley, Lawrence Berkeley National Laboratory, Raymond, Kenneth, Pluth, Michael D, Tiedemann, Bryan E.F., van Halbeek, Herman, Nunlist, Rudi, & Raymond, Kenneth N. Diffusion of a Highly-Charged Supramolecular Assembly: Direct Observation of Ion-Association in Water. United States.
University of California, Berkeley, Lawrence Berkeley National Laboratory, Raymond, Kenneth, Pluth, Michael D, Tiedemann, Bryan E.F., van Halbeek, Herman, Nunlist, Rudi, and Raymond, Kenneth N. Mon . "Diffusion of a Highly-Charged Supramolecular Assembly: Direct Observation of Ion-Association in Water". United States. https://www.osti.gov/servlets/purl/928951.
@article{osti_928951,
title = {Diffusion of a Highly-Charged Supramolecular Assembly: Direct Observation of Ion-Association in Water},
author = {University of California, Berkeley and Lawrence Berkeley National Laboratory and Raymond, Kenneth and Pluth, Michael D and Tiedemann, Bryan E.F. and van Halbeek, Herman and Nunlist, Rudi and Raymond, Kenneth N},
abstractNote = {Understanding the solution behavior of supramolecular assemblies is essential for a full understanding of the formation and chemistry of synthetic host-guest systems. While the interaction between host and guest molecules is generally the focus of mechanistic studies of host-guest complexes, the interaction of the host-guest complex with other species in solution remains largely unknown, although in principle accessible by diffusion studies. Several NMR techniques are available to monitor diffusion and have recently been reviewed. Pulsed gradient spin-echo (PGSE) NMR methods have attracted increasing interest, since they allow diffusion coefficients to be measured with high accuracy; they have been successfully used with observation of {sup 7}Li and {sup 31}P nuclei as well as with {sup 1}H NMR. We report here the direct measurement of diffusion coefficients to observe ion-association interactions by counter cations with a highly-charged supramolecular assembly. Raymond and coworkers have described the design and chemistry of a class of metal-ligand supramolecular assemblies over the past decade. The [Ga{sub 4}L{sub 6}]{sup 12-} (L = 1,5-bis(2,3-dihydroxybenzamido)naphthalene) (1) (Figure 1) assembly has garnered the most attention, with the exploration of the dynamics and mechanism of guest exchange as well as the ability of 1 to achieve either stoichiometric or catalytic reactions inside its interior cavity. Recent studies have revealed the importance of counter cations in solution on the chemistry of 1. During the mechanistic study of the C-H bond activation of aldehydes by [Cp*Ir(PMe{sub 3})(olefin){sup +} {contained_in} 1]{sup 11-} a stepwise guest dissociation mechanism with an ion-paired intermediate was proposed. Similarly, in the mechanism for the hydrolysis of iminium cations generated from the 3-aza Cope rearrangement of enammonium cations in 1, the presence of an exterior ion association was part of the kinetic model. To further substantiate the indirect kinetic evidence for such ion-paired species, we sought to explore the solution behavior of 1 by studying the diffusion of 1 with varying alkali and tetraalkyl ammonium cations. For large molecules in solution, such as synthetic supramolecular assemblies, the diffusion behavior of host and guest molecules can provide valuable information on host-guest interaction. One characteristic feature of a stable host-guest complex is that the host and guest molecules diffuse at the same rate in solution; this has been observed in a number of supramolecular systems. In order to confirm that this system was suitable for study by diffusion NMR spectroscopy, a PGSE-DOSY spectrum was acquired of [NEt{sub 4} {contained_in} 1]{sup 11-} (Figure 2), which shows that the host and guest molecules diffuse at the same rate. Quantitative analysis of the data, from monitoring the integral of host and guest resonances as a function of applied gradient strength, gave identical diffusion coefficients, confirming that the host and guest molecules diffuse together.},
doi = {},
url = {https://www.osti.gov/biblio/928951}, journal = {Inorganic Chemistry},
issn = {0020-1669},
number = ,
volume = 47,
place = {United States},
year = {2007},
month = {10}
}