Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {FeIII3} and {FeIII2CoII} pivalate spin clusters

Olga Botezat; Jan Van Leusen; Victor Ch Kravtsov; Irina G. Filippova; Jürg Hauser; Manfred Speldrich; Raphaël P. Hermann; Karl W. Krämer; Shi Xia Liu; Silvio Decurtins; Paul Kögerler; Svetlana G. Baca

doi:10.1021/cg5008236

Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {Fe^III₃} and {Fe^III₂Co^II} pivalate spin clusters

Olga Botezat, Jan Van Leusen, Victor Ch Kravtsov, Irina G. Filippova, Jürg Hauser, Manfred Speldrich, Raphaël P. Hermann, Karl W. Krämer, Shi Xia Liu, Silvio Decurtins, Paul Kögerler, Svetlana G. Baca

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Abstract

Two new magnetic cluster-based 3D coordination polymers consisting of μ₃-oxo-centered cationic homometallic [Fe^III ₃O(O₂CCMe₃)₆]⁺ or neutral heterometallic [Fe^III₂Co^IIO(O ₂CCMe₃)₆] coordination clusters bridged by different N,N′-donor ligands into three-dimensional networks of {[Fe ₃O(O₂CCMe₃)₆(4,4′-bpy) _1.5](OH)·0.75(CH₂Cl₂)·x(H ₂O)}_n (1, x ≤ 8) and {[Fe₂CoO(O ₂CCMe₃)₆(bpe)_0.5(pyz)]}_n (2) (where 4,4′-bpy = 4,4′-bipyridine; bpe = 1,2′-bis(4- pyridyl)ethylene; pyz = pyrazine) have been prepared under solvothermal conditions. Single-crystal X-ray diffraction studies reveal the existence of a 6-fold interpenetrated network with rare (8,3)-c (etc) topology for 1 and a 3-fold interpenetrated network with (10,3)-b (ths) topology for 2. The interpenetration effectively results in very low BET surface areas, and the compounds have to be regarded as nonporous. Magnetic studies of 1 and 2 point to both ferro- and antiferromagnetic intra- and intercluster exchange interactions between the isotropic Fe^III and the strongly anisotropic Co ^II spin centers. ⁵⁷Fe Mössbauer spectroscopy confirms the uniform ferric (+III) valence state in both 1 and 2, and low-temperature data for 1 point toward distinct hyperfine fields for the Fe sites.

Original language	English
Pages (from-to)	4721-4728
Number of pages	8
Journal	Crystal Growth and Design
Volume	14
Issue number	9
DOIs	https://doi.org/10.1021/cg5008236
State	Published - Sep 3 2014
Externally published	Yes

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10.1021/cg5008236

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Botezat, O., Van Leusen, J., Kravtsov, V. C., Filippova, I. G., Hauser, J., Speldrich, M., Hermann, R. P., Krämer, K. W., Liu, S. X., Decurtins, S., Kögerler, P., & Baca, S. G. (2014). Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {Fe^III₃} and {Fe^III₂Co^II} pivalate spin clusters. Crystal Growth and Design, 14(9), 4721-4728. https://doi.org/10.1021/cg5008236

@article{85ed773cc13e41cbb479206cd81118fe,

title = "Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {FeIII3} and {FeIII2CoII} pivalate spin clusters",

abstract = "Two new magnetic cluster-based 3D coordination polymers consisting of μ3-oxo-centered cationic homometallic [FeIII 3O(O2CCMe3)6]+ or neutral heterometallic [FeIII2CoIIO(O 2CCMe3)6] coordination clusters bridged by different N,N′-donor ligands into three-dimensional networks of {[Fe 3O(O2CCMe3)6(4,4′-bpy) 1.5](OH)·0.75(CH2Cl2)·x(H 2O)}n (1, x ≤ 8) and {[Fe2CoO(O 2CCMe3)6(bpe)0.5(pyz)]}n (2) (where 4,4′-bpy = 4,4′-bipyridine; bpe = 1,2′-bis(4- pyridyl)ethylene; pyz = pyrazine) have been prepared under solvothermal conditions. Single-crystal X-ray diffraction studies reveal the existence of a 6-fold interpenetrated network with rare (8,3)-c (etc) topology for 1 and a 3-fold interpenetrated network with (10,3)-b (ths) topology for 2. The interpenetration effectively results in very low BET surface areas, and the compounds have to be regarded as nonporous. Magnetic studies of 1 and 2 point to both ferro- and antiferromagnetic intra- and intercluster exchange interactions between the isotropic FeIII and the strongly anisotropic Co II spin centers. 57Fe M{\"o}ssbauer spectroscopy confirms the uniform ferric (+III) valence state in both 1 and 2, and low-temperature data for 1 point toward distinct hyperfine fields for the Fe sites.",

author = "Olga Botezat and {Van Leusen}, Jan and Kravtsov, {Victor Ch} and Filippova, {Irina G.} and J{\"u}rg Hauser and Manfred Speldrich and Hermann, {Rapha{\"e}l P.} and Kr{\"a}mer, {Karl W.} and Liu, {Shi Xia} and Silvio Decurtins and Paul K{\"o}gerler and Baca, {Svetlana G.}",

year = "2014",

month = sep,

day = "3",

doi = "10.1021/cg5008236",

language = "English",

volume = "14",

pages = "4721--4728",

journal = "Crystal Growth and Design",

issn = "1528-7483",

publisher = "American Chemical Society",

number = "9",

}

Botezat, O, Van Leusen, J, Kravtsov, VC, Filippova, IG, Hauser, J, Speldrich, M, Hermann, RP, Krämer, KW, Liu, SX, Decurtins, S, Kögerler, P & Baca, SG 2014, 'Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {Fe^III₃} and {Fe^III₂Co^II} pivalate spin clusters', Crystal Growth and Design, vol. 14, no. 9, pp. 4721-4728. https://doi.org/10.1021/cg5008236

TY - JOUR

T1 - Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {FeIII3} and {FeIII2CoII} pivalate spin clusters

AU - Botezat, Olga

AU - Van Leusen, Jan

AU - Kravtsov, Victor Ch

AU - Filippova, Irina G.

AU - Hauser, Jürg

AU - Speldrich, Manfred

AU - Hermann, Raphaël P.

AU - Krämer, Karl W.

AU - Liu, Shi Xia

AU - Decurtins, Silvio

AU - Kögerler, Paul

AU - Baca, Svetlana G.

PY - 2014/9/3

Y1 - 2014/9/3

N2 - Two new magnetic cluster-based 3D coordination polymers consisting of μ3-oxo-centered cationic homometallic [FeIII 3O(O2CCMe3)6]+ or neutral heterometallic [FeIII2CoIIO(O 2CCMe3)6] coordination clusters bridged by different N,N′-donor ligands into three-dimensional networks of {[Fe 3O(O2CCMe3)6(4,4′-bpy) 1.5](OH)·0.75(CH2Cl2)·x(H 2O)}n (1, x ≤ 8) and {[Fe2CoO(O 2CCMe3)6(bpe)0.5(pyz)]}n (2) (where 4,4′-bpy = 4,4′-bipyridine; bpe = 1,2′-bis(4- pyridyl)ethylene; pyz = pyrazine) have been prepared under solvothermal conditions. Single-crystal X-ray diffraction studies reveal the existence of a 6-fold interpenetrated network with rare (8,3)-c (etc) topology for 1 and a 3-fold interpenetrated network with (10,3)-b (ths) topology for 2. The interpenetration effectively results in very low BET surface areas, and the compounds have to be regarded as nonporous. Magnetic studies of 1 and 2 point to both ferro- and antiferromagnetic intra- and intercluster exchange interactions between the isotropic FeIII and the strongly anisotropic Co II spin centers. 57Fe Mössbauer spectroscopy confirms the uniform ferric (+III) valence state in both 1 and 2, and low-temperature data for 1 point toward distinct hyperfine fields for the Fe sites.

AB - Two new magnetic cluster-based 3D coordination polymers consisting of μ3-oxo-centered cationic homometallic [FeIII 3O(O2CCMe3)6]+ or neutral heterometallic [FeIII2CoIIO(O 2CCMe3)6] coordination clusters bridged by different N,N′-donor ligands into three-dimensional networks of {[Fe 3O(O2CCMe3)6(4,4′-bpy) 1.5](OH)·0.75(CH2Cl2)·x(H 2O)}n (1, x ≤ 8) and {[Fe2CoO(O 2CCMe3)6(bpe)0.5(pyz)]}n (2) (where 4,4′-bpy = 4,4′-bipyridine; bpe = 1,2′-bis(4- pyridyl)ethylene; pyz = pyrazine) have been prepared under solvothermal conditions. Single-crystal X-ray diffraction studies reveal the existence of a 6-fold interpenetrated network with rare (8,3)-c (etc) topology for 1 and a 3-fold interpenetrated network with (10,3)-b (ths) topology for 2. The interpenetration effectively results in very low BET surface areas, and the compounds have to be regarded as nonporous. Magnetic studies of 1 and 2 point to both ferro- and antiferromagnetic intra- and intercluster exchange interactions between the isotropic FeIII and the strongly anisotropic Co II spin centers. 57Fe Mössbauer spectroscopy confirms the uniform ferric (+III) valence state in both 1 and 2, and low-temperature data for 1 point toward distinct hyperfine fields for the Fe sites.

UR - http://www.scopus.com/inward/record.url?scp=84906862035&partnerID=8YFLogxK

U2 - 10.1021/cg5008236

DO - 10.1021/cg5008236

M3 - Article

AN - SCOPUS:84906862035

SN - 1528-7483

VL - 14

SP - 4721

EP - 4728

JO - Crystal Growth and Design

JF - Crystal Growth and Design

IS - 9

ER -

Interpenetrated (8,3)-c and (10,3)-b metal-organic frameworks based on {Fe^III₃} and {Fe^III₂Co^II} pivalate spin clusters

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