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Molecules 2018, 23(4), 858; doi:10.3390/molecules23040858

Confinement Effects on Chemical Equilibria: Pentacyano(Pyrazine)Ferrate(II) Stability Changes within Nanosized Droplets of Water

1
Department of Chemistry & Biochemistry, New Mexico State University, Las Cruces, NM 88003, USA
2
Department of Chemistry, Colorado State University, Ft. Collins, CO 80523, USA
*
Authors to whom correspondence should be addressed.
Academic Editors: Pallavincini Piersandro and Giacomo Dacarro
Received: 5 March 2018 / Revised: 30 March 2018 / Accepted: 4 April 2018 / Published: 9 April 2018
(This article belongs to the Special Issue Coordination Chemistry for Devices and Functional Materials)
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Abstract

Nanoscale confinement is known to impact properties of molecules and we observed changes in the reactivity of an iron coordination complex, pentacyano(pyrazine)ferrate(II). The confinement of two coordination complexes in a sodium AOT/isooctane reverse micellar (RM) water droplet was found to dramatically increase the hydrolysis rate of [Fe(CN)5pyz]3− and change the monomer-dimer equilibria between [Fe(CN)5pyz]3− and [Fe2(CN)10pyz]6−. Combined UV-Vis and 1H-NMR spectra of these complexes in RMs were analyzed and the position of the monomer-dimer equilibrium and the relative reaction times were determined at three different RM sizes. The data show that the hydrolysis rates (loss of pyrazine) are dramatically enhanced in RMs over bulk water and increase as the size of the RM decreases. Likewise, the monomer-dimer equilibrium changes to favor the formation of dimer as the RM size decreases. We conclude that the effects of the [Fe(CN)5pyz]3− stability is related to its solvation within the RM. View Full-Text
Keywords: Confinement effects; coordination chemistry at the nanoscale; pentacyano(pyrazine)ferrate(II); [Fe(CN)5pyz]3−; hydrolysis rates; monomer-dimer equilibrium; reverse micelles; interface interactions Confinement effects; coordination chemistry at the nanoscale; pentacyano(pyrazine)ferrate(II); [Fe(CN)5pyz]3−; hydrolysis rates; monomer-dimer equilibrium; reverse micelles; interface interactions
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Borunda, T.; Myers, A.J.; Mary Fisher, J.; Crans, D.C.; Johnson, M.D. Confinement Effects on Chemical Equilibria: Pentacyano(Pyrazine)Ferrate(II) Stability Changes within Nanosized Droplets of Water. Molecules 2018, 23, 858.

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