Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics

Matthew A.D. Roxburgh; Samantha Zaiter; Xina I.B. Hudson; Benjamin R. Mullaney; John E. Clements; Boujemaa Moubaraki; Keith S. Murray; Suzanne M. Neville; Cameron J. Kepert

doi:10.1071/CH16586

Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics

Matthew A.D. Roxburgh, Samantha Zaiter, Xina I.B. Hudson, Benjamin R. Mullaney, John E. Clements, Boujemaa Moubaraki, Keith S. Murray, Suzanne M. Neville, Cameron J. Kepert

School of Chemistry

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4 Citations (Scopus)

Abstract

Targeting the general (4,4)-grid structural motif, we have prepared seven new coordination polymers in the general family [Fe(NCX)₂(L)₂].(guest) (L=bis-pyridyl-type bridging ligands; X=S, Se) as an extension of the well-established spin crossover framework (SCOF) family. In all cases, the (4,4)-grid topology is formed by the bridging of octahedral iron(ii) sites in the equatorial plane by bis-pyridyl ligands of varying length, flexibility, and intermolecular interaction capacity. In particular, the six ligands n-(4-pyridyl)-isonicotinamide (pin), trans-1,2-bis(4′-pyridyl)ethane (tvp), 1,2-dibromo-1,2-bis(4′-pyridyl)ethane (dbbpe), bis(4-pyridyl)-1,2,4,5-tetrazine (bptz), 4,4′-bis(pyridyl)acetylene (bpac), and 1,4-bis(4-pyridylethynyl)benzene (bpeben) have been utilised. The seven new materials [Fe(NCS)₂(pin)₂].2(MeCN) (pin-S), [Fe(tvp)₂(NCS)₂].1/2(tvp).(CH₃CH₂OH) (tvp-S), [Fe(dbbpe)₂(NCS)₂].6(CH₃CN) (dbbpe-S), [Fe(NCS)₂(bptz)₂].2(CHCl₃).6(EtOH) (bptz-S), [Fe(NCSe)₂(bptz)₂].4(CHCl₃).(EtOH).(H₂O) (bptz-Se), [Fe(NCS)₂(bpac)₂].2(PrOH) (bpac-S), and [Fe(NCS)₂(bpeben)₂].2(CHCl₃) (bpeben-S) all form (4,4)-grids of varying size that are arranged in a parallel stacked topology. Despite being in the [FeN₆] coordination environment known to be conducive to spin crossover, these materials all remain high-spin with thermal variation. These results are discussed in context with the large family of SCOFs that show varied spin crossover behaviours.

Original language	English
Pages (from-to)	623-631
Number of pages	9
Journal	Australian Journal of Chemistry
Volume	70
Issue number	5
DOIs	https://doi.org/10.1071/CH16586
Publication status	Published - 1 Jan 2017

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10.1071/CH16586

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@article{fb519bff079040a497986063affc73b0,

title = "Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics",

abstract = "Targeting the general (4,4)-grid structural motif, we have prepared seven new coordination polymers in the general family [Fe(NCX)2(L)2].(guest) (L=bis-pyridyl-type bridging ligands; X=S, Se) as an extension of the well-established spin crossover framework (SCOF) family. In all cases, the (4,4)-grid topology is formed by the bridging of octahedral iron(ii) sites in the equatorial plane by bis-pyridyl ligands of varying length, flexibility, and intermolecular interaction capacity. In particular, the six ligands n-(4-pyridyl)-isonicotinamide (pin), trans-1,2-bis(4′-pyridyl)ethane (tvp), 1,2-dibromo-1,2-bis(4′-pyridyl)ethane (dbbpe), bis(4-pyridyl)-1,2,4,5-tetrazine (bptz), 4,4′-bis(pyridyl)acetylene (bpac), and 1,4-bis(4-pyridylethynyl)benzene (bpeben) have been utilised. The seven new materials [Fe(NCS)2(pin)2].2(MeCN) (pin-S), [Fe(tvp)2(NCS)2].1/2(tvp).(CH3CH2OH) (tvp-S), [Fe(dbbpe)2(NCS)2].6(CH3CN) (dbbpe-S), [Fe(NCS)2(bptz)2].2(CHCl3).6(EtOH) (bptz-S), [Fe(NCSe)2(bptz)2].4(CHCl3).(EtOH).(H2O) (bptz-Se), [Fe(NCS)2(bpac)2].2(PrOH) (bpac-S), and [Fe(NCS)2(bpeben)2].2(CHCl3) (bpeben-S) all form (4,4)-grids of varying size that are arranged in a parallel stacked topology. Despite being in the [FeN6] coordination environment known to be conducive to spin crossover, these materials all remain high-spin with thermal variation. These results are discussed in context with the large family of SCOFs that show varied spin crossover behaviours.",

author = "Roxburgh, {Matthew A.D.} and Samantha Zaiter and Hudson, {Xina I.B.} and Mullaney, {Benjamin R.} and Clements, {John E.} and Boujemaa Moubaraki and Murray, {Keith S.} and Neville, {Suzanne M.} and Kepert, {Cameron J.}",

year = "2017",

month = jan,

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doi = "10.1071/CH16586",

language = "English",

volume = "70",

pages = "623--631",

journal = "Australian Journal of Chemistry",

issn = "0004-9425",

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TY - JOUR

T1 - Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics

AU - Roxburgh, Matthew A.D.

AU - Zaiter, Samantha

AU - Hudson, Xina I.B.

AU - Mullaney, Benjamin R.

AU - Clements, John E.

AU - Moubaraki, Boujemaa

AU - Murray, Keith S.

AU - Neville, Suzanne M.

AU - Kepert, Cameron J.

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Targeting the general (4,4)-grid structural motif, we have prepared seven new coordination polymers in the general family [Fe(NCX)2(L)2].(guest) (L=bis-pyridyl-type bridging ligands; X=S, Se) as an extension of the well-established spin crossover framework (SCOF) family. In all cases, the (4,4)-grid topology is formed by the bridging of octahedral iron(ii) sites in the equatorial plane by bis-pyridyl ligands of varying length, flexibility, and intermolecular interaction capacity. In particular, the six ligands n-(4-pyridyl)-isonicotinamide (pin), trans-1,2-bis(4′-pyridyl)ethane (tvp), 1,2-dibromo-1,2-bis(4′-pyridyl)ethane (dbbpe), bis(4-pyridyl)-1,2,4,5-tetrazine (bptz), 4,4′-bis(pyridyl)acetylene (bpac), and 1,4-bis(4-pyridylethynyl)benzene (bpeben) have been utilised. The seven new materials [Fe(NCS)2(pin)2].2(MeCN) (pin-S), [Fe(tvp)2(NCS)2].1/2(tvp).(CH3CH2OH) (tvp-S), [Fe(dbbpe)2(NCS)2].6(CH3CN) (dbbpe-S), [Fe(NCS)2(bptz)2].2(CHCl3).6(EtOH) (bptz-S), [Fe(NCSe)2(bptz)2].4(CHCl3).(EtOH).(H2O) (bptz-Se), [Fe(NCS)2(bpac)2].2(PrOH) (bpac-S), and [Fe(NCS)2(bpeben)2].2(CHCl3) (bpeben-S) all form (4,4)-grids of varying size that are arranged in a parallel stacked topology. Despite being in the [FeN6] coordination environment known to be conducive to spin crossover, these materials all remain high-spin with thermal variation. These results are discussed in context with the large family of SCOFs that show varied spin crossover behaviours.

AB - Targeting the general (4,4)-grid structural motif, we have prepared seven new coordination polymers in the general family [Fe(NCX)2(L)2].(guest) (L=bis-pyridyl-type bridging ligands; X=S, Se) as an extension of the well-established spin crossover framework (SCOF) family. In all cases, the (4,4)-grid topology is formed by the bridging of octahedral iron(ii) sites in the equatorial plane by bis-pyridyl ligands of varying length, flexibility, and intermolecular interaction capacity. In particular, the six ligands n-(4-pyridyl)-isonicotinamide (pin), trans-1,2-bis(4′-pyridyl)ethane (tvp), 1,2-dibromo-1,2-bis(4′-pyridyl)ethane (dbbpe), bis(4-pyridyl)-1,2,4,5-tetrazine (bptz), 4,4′-bis(pyridyl)acetylene (bpac), and 1,4-bis(4-pyridylethynyl)benzene (bpeben) have been utilised. The seven new materials [Fe(NCS)2(pin)2].2(MeCN) (pin-S), [Fe(tvp)2(NCS)2].1/2(tvp).(CH3CH2OH) (tvp-S), [Fe(dbbpe)2(NCS)2].6(CH3CN) (dbbpe-S), [Fe(NCS)2(bptz)2].2(CHCl3).6(EtOH) (bptz-S), [Fe(NCSe)2(bptz)2].4(CHCl3).(EtOH).(H2O) (bptz-Se), [Fe(NCS)2(bpac)2].2(PrOH) (bpac-S), and [Fe(NCS)2(bpeben)2].2(CHCl3) (bpeben-S) all form (4,4)-grids of varying size that are arranged in a parallel stacked topology. Despite being in the [FeN6] coordination environment known to be conducive to spin crossover, these materials all remain high-spin with thermal variation. These results are discussed in context with the large family of SCOFs that show varied spin crossover behaviours.

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U2 - 10.1071/CH16586

DO - 10.1071/CH16586

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VL - 70

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JO - Australian Journal of Chemistry

JF - Australian Journal of Chemistry

SN - 0004-9425

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ER -

Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics

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Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics

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