Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior

Jong Won Shin; Ah Rim Jeong; Jong Hwa Jeong; Hikaru Zenno; Shinya Hayami; Kil Sik Min

doi:10.1039/c9ra09782a

Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior

Jong Won Shin, Ah Rim Jeong, Jong Hwa Jeong, Hikaru Zenno, Shinya Hayami, Kil Sik Min

Department of Chemical Science Education

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

7 Scopus citations

Abstract

Two Fe(ii)-based coordination polymers [Fe(tpmd)₂(NCS)₂]·5.5H₂O (1) and [Fe(tpmd)₂(NCSe)₂]·7H₂O (2) with the framework of square-grid type have been assembled from FeSO₄·7H₂O, N,N,N′,N′-tetrakis(pyridin-4-yl)methanediamine (tpmd), and KNCS/KNCSe in methanol and characterized. By utilizing two pyridine groups of a tpmd ligand, 1 and 2 are formed in two-dimensional layered structures through coordination of octahedral iron(ii) ions with the tpmd to NCS^-/NCSe^- ligands in which they have a supramolecular isomorphous conformation. 1 shows a paramagnetic behavior between 2 and 300 K, while 2 exhibits two-step spin crossover (ca. 145 and 50 K) in the temperature range due to the coordination of NCSe^- ligands. At 300 K 2 is fully high-spin state. However, at 100 K 2 becomes ca. 50% high spin and 50% low spin iron(ii) ions, which is verified by magnetic moments. In the structural analysis of 2 at 100 K, two different layers are observed with different bond distances around iron(ii) ions in which the layers are stacked alternately.

Original language	English
Pages (from-to)	5040-5049
Number of pages	10
Journal	RSC Advances
Volume	10
Issue number	9
DOIs	https://doi.org/10.1039/c9ra09782a
State	Published - 2020

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@article{47cceabb0021492a95e42c9487e9953e,

title = "Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior",

abstract = "Two Fe(ii)-based coordination polymers [Fe(tpmd)2(NCS)2]·5.5H2O (1) and [Fe(tpmd)2(NCSe)2]·7H2O (2) with the framework of square-grid type have been assembled from FeSO4·7H2O, N,N,N′,N′-tetrakis(pyridin-4-yl)methanediamine (tpmd), and KNCS/KNCSe in methanol and characterized. By utilizing two pyridine groups of a tpmd ligand, 1 and 2 are formed in two-dimensional layered structures through coordination of octahedral iron(ii) ions with the tpmd to NCS-/NCSe- ligands in which they have a supramolecular isomorphous conformation. 1 shows a paramagnetic behavior between 2 and 300 K, while 2 exhibits two-step spin crossover (ca. 145 and 50 K) in the temperature range due to the coordination of NCSe- ligands. At 300 K 2 is fully high-spin state. However, at 100 K 2 becomes ca. 50% high spin and 50% low spin iron(ii) ions, which is verified by magnetic moments. In the structural analysis of 2 at 100 K, two different layers are observed with different bond distances around iron(ii) ions in which the layers are stacked alternately.",

author = "Shin, {Jong Won} and Jeong, {Ah Rim} and Jeong, {Jong Hwa} and Hikaru Zenno and Shinya Hayami and Min, {Kil Sik}",

note = "Publisher Copyright: This journal is {\textcopyright} The Royal Society of Chemistry.",

year = "2020",

doi = "10.1039/c9ra09782a",

language = "English",

volume = "10",

pages = "5040--5049",

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T1 - Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior

AU - Shin, Jong Won

AU - Jeong, Ah Rim

AU - Jeong, Jong Hwa

AU - Zenno, Hikaru

AU - Hayami, Shinya

AU - Min, Kil Sik

PY - 2020

Y1 - 2020

N2 - Two Fe(ii)-based coordination polymers [Fe(tpmd)2(NCS)2]·5.5H2O (1) and [Fe(tpmd)2(NCSe)2]·7H2O (2) with the framework of square-grid type have been assembled from FeSO4·7H2O, N,N,N′,N′-tetrakis(pyridin-4-yl)methanediamine (tpmd), and KNCS/KNCSe in methanol and characterized. By utilizing two pyridine groups of a tpmd ligand, 1 and 2 are formed in two-dimensional layered structures through coordination of octahedral iron(ii) ions with the tpmd to NCS-/NCSe- ligands in which they have a supramolecular isomorphous conformation. 1 shows a paramagnetic behavior between 2 and 300 K, while 2 exhibits two-step spin crossover (ca. 145 and 50 K) in the temperature range due to the coordination of NCSe- ligands. At 300 K 2 is fully high-spin state. However, at 100 K 2 becomes ca. 50% high spin and 50% low spin iron(ii) ions, which is verified by magnetic moments. In the structural analysis of 2 at 100 K, two different layers are observed with different bond distances around iron(ii) ions in which the layers are stacked alternately.

AB - Two Fe(ii)-based coordination polymers [Fe(tpmd)2(NCS)2]·5.5H2O (1) and [Fe(tpmd)2(NCSe)2]·7H2O (2) with the framework of square-grid type have been assembled from FeSO4·7H2O, N,N,N′,N′-tetrakis(pyridin-4-yl)methanediamine (tpmd), and KNCS/KNCSe in methanol and characterized. By utilizing two pyridine groups of a tpmd ligand, 1 and 2 are formed in two-dimensional layered structures through coordination of octahedral iron(ii) ions with the tpmd to NCS-/NCSe- ligands in which they have a supramolecular isomorphous conformation. 1 shows a paramagnetic behavior between 2 and 300 K, while 2 exhibits two-step spin crossover (ca. 145 and 50 K) in the temperature range due to the coordination of NCSe- ligands. At 300 K 2 is fully high-spin state. However, at 100 K 2 becomes ca. 50% high spin and 50% low spin iron(ii) ions, which is verified by magnetic moments. In the structural analysis of 2 at 100 K, two different layers are observed with different bond distances around iron(ii) ions in which the layers are stacked alternately.

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U2 - 10.1039/c9ra09782a

DO - 10.1039/c9ra09782a

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VL - 10

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EP - 5049

JO - RSC Advances

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Two-dimensional square-grid iron(ii) coordination polymers showing anion-dependent spin crossover behavior

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