Small-angle X-ray scattering (SAXS) studies of aqueous [Ta6O19]8−
compared to prior studies of aq... more Small-angle X-ray scattering (SAXS) studies of aqueous [Ta6O19]8− compared to prior studies of aqueous [Nb6O19]8− reveals key differences in behaviour, which is likely at the root of the difficultly in developing polyoxotantalate chemistry. Specifically, where contact ion-pairing dominates between [Nb6O19]8− and its counterions, solvent-separated ion-pairing between [Ta6O19]8− and its counterions has been unveiled in the current study.
Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII
13P8W60O227(OH)15(H2O)2]30− (1) a... more Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII 13P8W60O227(OH)15(H2O)2]30− (1) and [FeIII 13P8W60O224(OH)12(PO4)4]33− (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor [α-P2W15O56]12− and FeCl3 under strict pH control at atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy) and in the gas phase (ESI-MS). An {FeIII 13} core is present in both clusters which can be described as Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery properties coupled to a K+-triggered transformation of the {Fe13} core to a {K⊂Fe12} core in solution. Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the gas phase.
Small-angle X-ray scattering (SAXS) studies of aqueous [Ta6O19]8−
compared to prior studies of aq... more Small-angle X-ray scattering (SAXS) studies of aqueous [Ta6O19]8− compared to prior studies of aqueous [Nb6O19]8− reveals key differences in behaviour, which is likely at the root of the difficultly in developing polyoxotantalate chemistry. Specifically, where contact ion-pairing dominates between [Nb6O19]8− and its counterions, solvent-separated ion-pairing between [Ta6O19]8− and its counterions has been unveiled in the current study.
Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII
13P8W60O227(OH)15(H2O)2]30− (1) a... more Two nanosized 2.6 nm FeIII substituted polyoxotungstates [FeIII 13P8W60O227(OH)15(H2O)2]30− (1) and [FeIII 13P8W60O224(OH)12(PO4)4]33− (2) are presented herein. Both clusters are synthesized from the reactions of trilacunary polyoxotungstate precursor [α-P2W15O56]12− and FeCl3 under strict pH control at atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy) and in the gas phase (ESI-MS). An {FeIII 13} core is present in both clusters which can be described as Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery properties coupled to a K+-triggered transformation of the {Fe13} core to a {K⊂Fe12} core in solution. Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the gas phase.
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Papers by Pedro Molina Sanchez
compared to prior studies of aqueous [Nb6O19]8− reveals key
differences in behaviour, which is likely at the root of the difficultly
in developing polyoxotantalate chemistry. Specifically, where
contact ion-pairing dominates between [Nb6O19]8− and its
counterions, solvent-separated ion-pairing between [Ta6O19]8−
and its counterions has been unveiled in the current study.
13P8W60O227(OH)15(H2O)2]30− (1) and
[FeIII
13P8W60O224(OH)12(PO4)4]33− (2) are presented herein. Both clusters are synthesized from the reactions
of trilacunary polyoxotungstate precursor [α-P2W15O56]12− and FeCl3 under strict pH control at
atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal
XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy)
and in the gas phase (ESI-MS). An {FeIII
13} core is present in both clusters which can be described as
Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery
properties coupled to a K+-triggered transformation of the {Fe13} core to a {K⊂Fe12} core in solution.
Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support
the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the
gas phase.
compared to prior studies of aqueous [Nb6O19]8− reveals key
differences in behaviour, which is likely at the root of the difficultly
in developing polyoxotantalate chemistry. Specifically, where
contact ion-pairing dominates between [Nb6O19]8− and its
counterions, solvent-separated ion-pairing between [Ta6O19]8−
and its counterions has been unveiled in the current study.
13P8W60O227(OH)15(H2O)2]30− (1) and
[FeIII
13P8W60O224(OH)12(PO4)4]33− (2) are presented herein. Both clusters are synthesized from the reactions
of trilacunary polyoxotungstate precursor [α-P2W15O56]12− and FeCl3 under strict pH control at
atmospheric pressure. The compounds are fully characterised in the solid state (FTIR and single-crystal
XRD, elemental and thermogravimetric analyses), solution (cyclic voltammetry and UV-Vis spectroscopy)
and in the gas phase (ESI-MS). An {FeIII
13} core is present in both clusters which can be described as
Archimedean solids (truncated tetrahedron, 1; elongated cuboctahedron, 2). 1 shows iron delivery
properties coupled to a K+-triggered transformation of the {Fe13} core to a {K⊂Fe12} core in solution.
Cyclic voltammetry shows the presence of independent W- and Fe-centred redox processes that support
the stability of the clusters in solution. ESI-MS analyses confirm further the stability of 1 and 2 in the
gas phase.