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

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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 languageEnglish
Pages (from-to)623-631
Number of pages9
JournalAustralian Journal of Chemistry
Volume70
Issue number5
DOIs
Publication statusPublished - 1 Jan 2017

Cite this

Roxburgh, M. A. D., Zaiter, S., Hudson, X. I. B., Mullaney, B. R., Clements, J. E., Moubaraki, B., ... Kepert, C. J. (2017). Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics. Australian Journal of Chemistry, 70(5), 623-631. https://doi.org/10.1071/CH16586
Roxburgh, Matthew A.D. ; Zaiter, Samantha ; Hudson, Xina I.B. ; Mullaney, Benjamin R. ; Clements, John E. ; Moubaraki, Boujemaa ; Murray, Keith S. ; Neville, Suzanne M. ; Kepert, Cameron J. / Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics. In: Australian Journal of Chemistry. 2017 ; Vol. 70, No. 5. pp. 623-631.
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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.",
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Roxburgh, MAD, Zaiter, S, Hudson, XIB, Mullaney, BR, Clements, JE, Moubaraki, B, Murray, KS, Neville, SM & Kepert, CJ 2017, 'Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics' Australian Journal of Chemistry, vol. 70, no. 5, pp. 623-631. https://doi.org/10.1071/CH16586

Structure and Magnetic Studies on a Series of Two-Dimensional Iron(II) Framework Materials with Varying Ligand Characteristics. / Roxburgh, Matthew A.D.; Zaiter, Samantha; Hudson, Xina I.B.; Mullaney, Benjamin R.; Clements, John E.; Moubaraki, Boujemaa; Murray, Keith S.; Neville, Suzanne M.; Kepert, Cameron J.

In: Australian Journal of Chemistry, Vol. 70, No. 5, 01.01.2017, p. 623-631.

Research output: Contribution to journalArticleResearchpeer-review

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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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