1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect

Rachel Shaw; Rebecca H. Laye; Leigh F. Jones; David M. Low; Caytie Talbot-Eeckelaers; Qiang Wei; Constantinos J. Milios; Simon Teat; Madeleine Helliwell; James Raftery; Marco Evangelisti; Marco Affronte; David Collison; Euan K. Brechin; Eric J L McInnes

doi:10.1021/ic070320k

1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect

Rachel Shaw, Rebecca H. Laye, Leigh F. Jones, David M. Low, Caytie Talbot-Eeckelaers, Qiang Wei, Constantinos J. Milios, Simon Teat, Madeleine Helliwell, James Raftery, Marco Evangelisti, Marco Affronte, David Collison, Euan K. Brechin, Eric J L McInnes

Research output: Contribution to journal › Article › peer-review

Abstract

We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe) 18-Cl6] (M = FeIII, CrIII) and [V14(L)6O6(OMe)18Cl 6-xOx] (L = anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe 14(C2H2N3)6O 6(OMe)18Cl6], [Cr14(bta) 6O6(OMe)18Cl6] (btaH = benzotriazole), [V14O6(Me2bta) 6(OMe)18Cl6-xOx] [Me2btaH = 5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-CI}2+ and {V IV=O}2+] and for the distorted [FeIII 14O9(OH)(OMe)8(bta)7-(MeOH) 5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S ≤ 25, among the highest known, while in contrast the {Cr14} complex has an S = 0 ground state despite having a very similar structure and all complexes being dominated by intramolecular antiferromagnetic exchange interactions. The {Fe14} complexes undergo a magnetic phase transition to long-range ordering at relatively high temperatures for molecular species, which are governed by the steric bulk of the triazole (TN = 1.8 and 3.4 K for L = bta - and H2C2N3-, respectively). The huge spins of the {Fe14} complexes lead to very large magnetocaloric effects (MCE) - the largest known for any material below 10 K - which is further enhanced by spin frustration within the molecules due to the competing antiferromagnetic interactions. The largest MCE is found for [Fe14-(C2H2N3)6O 6(OMe)18Cl6] with an isothermal magnetic entropy change -ΔSm of 20.3 J kg-1 K-1 at 6 K for an applied magnetic field change of 0-7 T. © 2007 American Chemical Society.

Original language	English
Pages (from-to)	4968-4978
Number of pages	10
Journal	Inorganic Chemistry: including bioinorganic chemistry
Volume	46
Issue number	12
DOIs	https://doi.org/10.1021/ic070320k
Publication status	Published - 11 Jun 2007

Keywords

DODECANUCLEAR CHROMIUM(III) CAGE
SOLVOTHERMAL SYNTHESIS
HIGH-NUCLEARITY
WHEELS
MAGNETS
FAMILY

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CCDC 654399: Experimental Crystal Structure Determination
Shaw, R. (Contributor), Laye, R. H. (Contributor), Jones, L. F. (Contributor), Low, D. M. (Contributor), Talbot-Eeckelaers, C. (Contributor), Wei, Q. (Contributor), Milios, C. J. (Contributor), Teat, S. J. (Contributor), Helliwell, M. (Contributor), Raftery, J. (Contributor), Evangelisti, M. (Contributor), Affronte, M. (Contributor), Collison, D. (Contributor), Brechin, E. K. (Contributor) & Mcinnes, E. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2007
DOI: 10.5517/ccpyyn6, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpyyn6&sid=DataCite
Dataset
CCDC 654402: Experimental Crystal Structure Determination
Shaw, R. (Contributor), Laye, R. H. (Contributor), Jones, L. F. (Contributor), Low, D. M. (Contributor), Talbot-Eeckelaers, C. (Contributor), Wei, Q. (Contributor), Milios, C. J. (Contributor), Teat, S. J. (Contributor), Helliwell, M. (Contributor), Raftery, J. (Contributor), Evangelisti, M. (Contributor), Affronte, M. (Contributor), Collison, D. (Contributor), Brechin, E. K. (Contributor) & Mcinnes, E. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2007
DOI: 10.5517/ccpyyr9, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpyyr9&sid=DataCite
Dataset
CCDC 654401: Experimental Crystal Structure Determination
Shaw, R. (Contributor), Laye, R. H. (Contributor), Jones, L. F. (Contributor), Low, D. M. (Contributor), Talbot-Eeckelaers, C. (Contributor), Wei, Q. (Contributor), Milios, C. J. (Contributor), Teat, S. J. (Contributor), Helliwell, M. (Contributor), Raftery, J. (Contributor), Evangelisti, M. (Contributor), Affronte, M. (Contributor), Collison, D. (Contributor), Brechin, E. K. (Contributor) & Mcinnes, E. (Contributor), Cambridge Crystallographic Data Centre, 1 Jan 2007
DOI: 10.5517/ccpyyq8, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccpyyq8&sid=DataCite
Dataset

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Shaw, R., Laye, R. H., Jones, L. F., Low, D. M., Talbot-Eeckelaers, C., Wei, Q., Milios, C. J., Teat, S., Helliwell, M., Raftery, J., Evangelisti, M., Affronte, M., Collison, D., Brechin, E. K., & McInnes, E. J. L. (2007). 1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect. Inorganic Chemistry: including bioinorganic chemistry , 46(12), 4968-4978. https://doi.org/10.1021/ic070320k

Shaw, Rachel ; Laye, Rebecca H. ; Jones, Leigh F. et al. / 1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect. In: Inorganic Chemistry: including bioinorganic chemistry . 2007 ; Vol. 46, No. 12. pp. 4968-4978.

@article{c3aefdee61924595a688f2817f8ef90f,

title = "1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect",

abstract = "We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe) 18-Cl6] (M = FeIII, CrIII) and [V14(L)6O6(OMe)18Cl 6-xOx] (L = anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe 14(C2H2N3)6O 6(OMe)18Cl6], [Cr14(bta) 6O6(OMe)18Cl6] (btaH = benzotriazole), [V14O6(Me2bta) 6(OMe)18Cl6-xOx] [Me2btaH = 5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-CI}2+ and {V IV=O}2+] and for the distorted [FeIII 14O9(OH)(OMe)8(bta)7-(MeOH) 5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S ≤ 25, among the highest known, while in contrast the {Cr14} complex has an S = 0 ground state despite having a very similar structure and all complexes being dominated by intramolecular antiferromagnetic exchange interactions. The {Fe14} complexes undergo a magnetic phase transition to long-range ordering at relatively high temperatures for molecular species, which are governed by the steric bulk of the triazole (TN = 1.8 and 3.4 K for L = bta - and H2C2N3-, respectively). The huge spins of the {Fe14} complexes lead to very large magnetocaloric effects (MCE) - the largest known for any material below 10 K - which is further enhanced by spin frustration within the molecules due to the competing antiferromagnetic interactions. The largest MCE is found for [Fe14-(C2H2N3)6O 6(OMe)18Cl6] with an isothermal magnetic entropy change -ΔSm of 20.3 J kg-1 K-1 at 6 K for an applied magnetic field change of 0-7 T. {\textcopyright} 2007 American Chemical Society.",

keywords = "DODECANUCLEAR CHROMIUM(III) CAGE, SOLVOTHERMAL SYNTHESIS, HIGH-NUCLEARITY, WHEELS, MAGNETS, FAMILY",

author = "Rachel Shaw and Laye, {Rebecca H.} and Jones, {Leigh F.} and Low, {David M.} and Caytie Talbot-Eeckelaers and Qiang Wei and Milios, {Constantinos J.} and Simon Teat and Madeleine Helliwell and James Raftery and Marco Evangelisti and Marco Affronte and David Collison and Brechin, {Euan K.} and McInnes, {Eric J L}",

note = "Shaw, Rachel Laye, Rebecca H. Jones, Leigh F. Low, David M. Talbot-Eeckelaers, Caytie Wei, Qiang Milios, Constantinos J. Teat, Simon Helliwell, Madeleine Raftery, James Evangelisti, Marco Affronte, Marco Collison, David Brechin, Euan K. McInnes, Eric J. L. 33 AMER CHEMICAL SOC WASHINGTON 173YG",

year = "2007",

month = jun,

day = "11",

doi = "10.1021/ic070320k",

language = "English",

volume = "46",

pages = "4968--4978",

journal = "Inorganic Chemistry: including bioinorganic chemistry ",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "12",

}

Shaw, R, Laye, RH, Jones, LF, Low, DM, Talbot-Eeckelaers, C, Wei, Q, Milios, CJ, Teat, S, Helliwell, M, Raftery, J, Evangelisti, M, Affronte, M, Collison, D, Brechin, EK & McInnes, EJL 2007, '1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect', Inorganic Chemistry: including bioinorganic chemistry , vol. 46, no. 12, pp. 4968-4978. https://doi.org/10.1021/ic070320k

1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect. / Shaw, Rachel; Laye, Rebecca H.; Jones, Leigh F. et al.
In: Inorganic Chemistry: including bioinorganic chemistry , Vol. 46, No. 12, 11.06.2007, p. 4968-4978.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - 1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect

AU - Shaw, Rachel

AU - Laye, Rebecca H.

AU - Jones, Leigh F.

AU - Low, David M.

AU - Talbot-Eeckelaers, Caytie

AU - Wei, Qiang

AU - Milios, Constantinos J.

AU - Teat, Simon

AU - Helliwell, Madeleine

AU - Raftery, James

AU - Evangelisti, Marco

AU - Affronte, Marco

AU - Collison, David

AU - Brechin, Euan K.

AU - McInnes, Eric J L

N1 - Shaw, Rachel Laye, Rebecca H. Jones, Leigh F. Low, David M. Talbot-Eeckelaers, Caytie Wei, Qiang Milios, Constantinos J. Teat, Simon Helliwell, Madeleine Raftery, James Evangelisti, Marco Affronte, Marco Collison, David Brechin, Euan K. McInnes, Eric J. L. 33 AMER CHEMICAL SOC WASHINGTON 173YG

PY - 2007/6/11

Y1 - 2007/6/11

N2 - We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe) 18-Cl6] (M = FeIII, CrIII) and [V14(L)6O6(OMe)18Cl 6-xOx] (L = anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe 14(C2H2N3)6O 6(OMe)18Cl6], [Cr14(bta) 6O6(OMe)18Cl6] (btaH = benzotriazole), [V14O6(Me2bta) 6(OMe)18Cl6-xOx] [Me2btaH = 5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-CI}2+ and {V IV=O}2+] and for the distorted [FeIII 14O9(OH)(OMe)8(bta)7-(MeOH) 5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S ≤ 25, among the highest known, while in contrast the {Cr14} complex has an S = 0 ground state despite having a very similar structure and all complexes being dominated by intramolecular antiferromagnetic exchange interactions. The {Fe14} complexes undergo a magnetic phase transition to long-range ordering at relatively high temperatures for molecular species, which are governed by the steric bulk of the triazole (TN = 1.8 and 3.4 K for L = bta - and H2C2N3-, respectively). The huge spins of the {Fe14} complexes lead to very large magnetocaloric effects (MCE) - the largest known for any material below 10 K - which is further enhanced by spin frustration within the molecules due to the competing antiferromagnetic interactions. The largest MCE is found for [Fe14-(C2H2N3)6O 6(OMe)18Cl6] with an isothermal magnetic entropy change -ΔSm of 20.3 J kg-1 K-1 at 6 K for an applied magnetic field change of 0-7 T. © 2007 American Chemical Society.

AB - We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe) 18-Cl6] (M = FeIII, CrIII) and [V14(L)6O6(OMe)18Cl 6-xOx] (L = anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe 14(C2H2N3)6O 6(OMe)18Cl6], [Cr14(bta) 6O6(OMe)18Cl6] (btaH = benzotriazole), [V14O6(Me2bta) 6(OMe)18Cl6-xOx] [Me2btaH = 5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-CI}2+ and {V IV=O}2+] and for the distorted [FeIII 14O9(OH)(OMe)8(bta)7-(MeOH) 5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S ≤ 25, among the highest known, while in contrast the {Cr14} complex has an S = 0 ground state despite having a very similar structure and all complexes being dominated by intramolecular antiferromagnetic exchange interactions. The {Fe14} complexes undergo a magnetic phase transition to long-range ordering at relatively high temperatures for molecular species, which are governed by the steric bulk of the triazole (TN = 1.8 and 3.4 K for L = bta - and H2C2N3-, respectively). The huge spins of the {Fe14} complexes lead to very large magnetocaloric effects (MCE) - the largest known for any material below 10 K - which is further enhanced by spin frustration within the molecules due to the competing antiferromagnetic interactions. The largest MCE is found for [Fe14-(C2H2N3)6O 6(OMe)18Cl6] with an isothermal magnetic entropy change -ΔSm of 20.3 J kg-1 K-1 at 6 K for an applied magnetic field change of 0-7 T. © 2007 American Chemical Society.

KW - DODECANUCLEAR CHROMIUM(III) CAGE

KW - SOLVOTHERMAL SYNTHESIS

KW - HIGH-NUCLEARITY

KW - WHEELS

KW - MAGNETS

KW - FAMILY

U2 - 10.1021/ic070320k

DO - 10.1021/ic070320k

M3 - Article

SN - 0020-1669

VL - 46

SP - 4968

EP - 4978

JO - Inorganic Chemistry: including bioinorganic chemistry

JF - Inorganic Chemistry: including bioinorganic chemistry

IS - 12

ER -

Shaw R, Laye RH, Jones LF, Low DM, Talbot-Eeckelaers C, Wei Q et al. 1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect. Inorganic Chemistry: including bioinorganic chemistry . 2007 Jun 11;46(12):4968-4978. doi: 10.1021/ic070320k

1,2,3-Triazolate-bridged tetradecametallic transition metal clusters [M14(L)6O6(OMe)18X6] (M = FeIII, CrIII and VIII/IV) and related compounds: Ground-state spins ranging from S = 0 to S = 25 and spin-enhanced magnetocaloric effect

Abstract

Keywords

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Datasets

CCDC 654399: Experimental Crystal Structure Determination

CCDC 654402: Experimental Crystal Structure Determination

CCDC 654401: Experimental Crystal Structure Determination

Cite this