Abstract
| Language | English |
|---|---|
| Pages | 1475-1480 |
| Number of pages | 6 |
| Journal | Dalton Transactions |
| Volume | 41 |
| Issue number | 5 |
| DOIs | |
| Status | Published - 2012 |
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Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and surface conduction. / Halls, Jonathan E; Hernan-Gomez, A; Burrows, Andrew D; Marken, Frank.
In: Dalton Transactions, Vol. 41, No. 5, 2012, p. 1475-1480.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Metal-organic frameworks post-synthetically modified with ferrocenyl groups: framework effects on redox processes and surface conduction
AU - Halls,Jonathan E
AU - Hernan-Gomez,A
AU - Burrows,Andrew D
AU - Marken,Frank
PY - 2012
Y1 - 2012
N2 - Metal-organic framework (MOF) materials based on zinc(II) and aluminium(III) dicarboxylate frameworks with covalently attached ferrocene functional redox groups were synthesised by post-synthetic modification and investigated by voltammetry in aqueous and non-aqueous media. In the voltammetry experiments, ferrocene oxidation occurs in all cases, but chemically reversible and stable ferrocene oxidation without decay of the voltammetric response requires a "mild" dichloroethane solvent environment. The voltammetric response in this case is identified as "surface-confined" with fast surface-hopping of electrons and without affecting the bulk of MOF microcrystals. In aqueous media a more complex pH-dependent multi-stage redox process is observed associated with chemically irreversible bulk oxidation and disintegration of the MOF framework. A characteristic 30 mV per pH unit dependence of redox potentials is observed attributed to a "framework effect": the hydroxide-driven MOF framework dissolution.
AB - Metal-organic framework (MOF) materials based on zinc(II) and aluminium(III) dicarboxylate frameworks with covalently attached ferrocene functional redox groups were synthesised by post-synthetic modification and investigated by voltammetry in aqueous and non-aqueous media. In the voltammetry experiments, ferrocene oxidation occurs in all cases, but chemically reversible and stable ferrocene oxidation without decay of the voltammetric response requires a "mild" dichloroethane solvent environment. The voltammetric response in this case is identified as "surface-confined" with fast surface-hopping of electrons and without affecting the bulk of MOF microcrystals. In aqueous media a more complex pH-dependent multi-stage redox process is observed associated with chemically irreversible bulk oxidation and disintegration of the MOF framework. A characteristic 30 mV per pH unit dependence of redox potentials is observed attributed to a "framework effect": the hydroxide-driven MOF framework dissolution.
UR - http://www.scopus.com/inward/record.url?scp=84856711318&partnerID=8YFLogxK
UR - http://dx.doi.org/10.1039/c1dt10734h
U2 - 10.1039/c1dt10734h
DO - 10.1039/c1dt10734h
M3 - Article
VL - 41
SP - 1475
EP - 1480
JO - Dalton Transactions
T2 - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 5
ER -