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Modular [FeIII 8MII 6]n+ (MII = Pd, Co, Ni, Cu) coordination cages

Modular [FeIII 8MII 6]n+ (MII = Pd, Co, Ni, Cu) coordination cages
Modular [FeIII 8MII 6]n+ (MII = Pd, Co, Ni, Cu) coordination cages

The reaction of the simple metalloligand [FeIIIL3] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different MII salts results in the formation of a family of heterometallic cages of formulae [FeIII 8PdII 6L24]Cl12 (1), [FeIII 8CuII 6L24(H2O)4Br4]Br8 (2), [FeIII 8CuII 6L24(H2O)10](NO3)12 (3), [FeIII 8NiII 6L24(SCN)11Cl] (4), and [FeIII 8CoII 6L24(SCN)10(H2O)2]Cl2 (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3-5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine JFe-Cu = 0.10 cm-1 for 3 and JFe-Ni = 0.025 cm-1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the FeIII zero-field splitting is larger in the heterometallic cage than in the monomer.

0020-1669
3500-3506
Sanz, Sergio
d7d88bc7-d8c4-4003-818d-ce6bc965cbe9
O'Connor, Helen M.
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Comar, Priyanka
ca77be3b-67f1-437b-a98c-8ab6a29515d3
Baldansuren, Amgalanbaatar
7ba5322a-57a0-4b4b-9c90-ca2edf6ffb13
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Weihe, Høgni
170e792d-b85a-4e12-b8c0-d5afa41f292b
Chilton, Nicholas F.
850941d1-c8bf-40fd-abaa-6a5467a0e549
McInnes, Eric J.L.
bba4b839-d79c-4561-b6e7-c002cc251ff4
Lusby, Paul J.
7edd6163-af61-4425-83ef-bf48d9c9b094
Piligkos, Stergios
50cdf27a-f790-4aab-92e8-80d433567f4e
Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc
Sanz, Sergio
d7d88bc7-d8c4-4003-818d-ce6bc965cbe9
O'Connor, Helen M.
d826fdbd-f27d-4b62-b37f-7d4a551ee26b
Comar, Priyanka
ca77be3b-67f1-437b-a98c-8ab6a29515d3
Baldansuren, Amgalanbaatar
7ba5322a-57a0-4b4b-9c90-ca2edf6ffb13
Pitak, Mateusz B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Weihe, Høgni
170e792d-b85a-4e12-b8c0-d5afa41f292b
Chilton, Nicholas F.
850941d1-c8bf-40fd-abaa-6a5467a0e549
McInnes, Eric J.L.
bba4b839-d79c-4561-b6e7-c002cc251ff4
Lusby, Paul J.
7edd6163-af61-4425-83ef-bf48d9c9b094
Piligkos, Stergios
50cdf27a-f790-4aab-92e8-80d433567f4e
Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc

Sanz, Sergio, O'Connor, Helen M., Comar, Priyanka, Baldansuren, Amgalanbaatar, Pitak, Mateusz B., Coles, Simon J., Weihe, Høgni, Chilton, Nicholas F., McInnes, Eric J.L., Lusby, Paul J., Piligkos, Stergios and Brechin, Euan K. (2018) Modular [FeIII 8MII 6]n+ (MII = Pd, Co, Ni, Cu) coordination cages. Inorganic Chemistry, 57 (7), 3500-3506. (doi:10.1021/acs.inorgchem.7b02674).

Record type: Review

Abstract

The reaction of the simple metalloligand [FeIIIL3] [HL = 1-(4-pyridyl)butane-1,3-dione] with a variety of different MII salts results in the formation of a family of heterometallic cages of formulae [FeIII 8PdII 6L24]Cl12 (1), [FeIII 8CuII 6L24(H2O)4Br4]Br8 (2), [FeIII 8CuII 6L24(H2O)10](NO3)12 (3), [FeIII 8NiII 6L24(SCN)11Cl] (4), and [FeIII 8CoII 6L24(SCN)10(H2O)2]Cl2 (5). The metallic skeleton of each cage describes a cube in which the FeIII ions occupy the eight vertices and the MII ions lie at the center of the six faces. Direct-current magnetic susceptibility and magnetization measurements on 3-5 reveal the presence of weak antiferromagnetic exchange between the metal ions in all three cases. Computational techniques known in theoretical nuclear physics as statistical spectroscopy, which exploit the moments of the Hamiltonian to calculate relevant thermodynamic properties, determine JFe-Cu = 0.10 cm-1 for 3 and JFe-Ni = 0.025 cm-1 for 4. Q-band electron paramagnetic resonance spectra of 1 reveal a significantly wider spectral width in comparison to [FeL3], indicating that the magnitude of the FeIII zero-field splitting is larger in the heterometallic cage than in the monomer.

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e-pub ahead of print date: 11 January 2018
Published date: 2 April 2018

Identifiers

Local EPrints ID: 419973
URI: https://eprints.soton.ac.uk/id/eprint/419973
ISSN: 0020-1669
PURE UUID: bc462ac6-003a-48a0-a956-3e4758bb9f35
ORCID for Mateusz B. Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

Catalogue record

Date deposited: 25 Apr 2018 16:30
Last modified: 06 Jun 2018 12:54

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Contributors

Author: Sergio Sanz
Author: Helen M. O'Connor
Author: Priyanka Comar
Author: Amgalanbaatar Baldansuren
Author: Mateusz B. Pitak ORCID iD
Author: Simon J. Coles ORCID iD
Author: Høgni Weihe
Author: Nicholas F. Chilton
Author: Eric J.L. McInnes
Author: Paul J. Lusby
Author: Stergios Piligkos
Author: Euan K. Brechin

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