Advanced search
1 file | 1.39 MB Add to list

Stabilization of the low-spin state in a mononuclear Iron(II) complex and high-temperature cooperative spin crossover mediated by hydrogen bonding

(2016) CHEMISTRY-A EUROPEAN JOURNAL. 22(1). p.331-339
Author
Organization
Abstract
The tetrapyridyl ligand bbpya (bbpya=N,N-bis(2,2'-bipyrid-6-yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)(2)] (1) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai's domain model, and powder X-ray diffraction measurements, 1 is low-spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T-1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong N-H center dot center dot center dot S intermolecular H-bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1. DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N'-di(pyrid-2yl)-2,2'-bipyridine-6,6'-diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)( NCS)(2)] (2). Periodic DFT calculations suggest that crystal-packing effects are significant for compound 2, in which they destabilize the HS state by about 1500 cm(-1). The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing.
Keywords
WIDE THERMAL HYSTERESIS, ROOM-TEMPERATURE, TRANSITION-TEMPERATURE, PERFORMANCE, VALIDATION, CHEMISTRY, INTERPLAY, POLYMERS, LIGANDS, SYSTEMS, cooperative effects, hydrogen bonds, iron, ligand design, spin crossover

Downloads

  • 15.pdf
    • full text
    • |
    • open access
    • |
    • PDF
    • |
    • 1.39 MB

Citation

Please use this url to cite or link to this publication:

MLA
Zheng, Sipeng, Niels RM Reintjens, Maxime A Siegler, et al. “Stabilization of the Low-spin State in a Mononuclear Iron(II) Complex and High-temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding.” CHEMISTRY-A EUROPEAN JOURNAL 22.1 (2016): 331–339. Print.
APA
Zheng, S., Reintjens, N. R., Siegler, M. A., Roubeau, O., Bouwman, E., Rudavskyi, A., Havenith, R., et al. (2016). Stabilization of the low-spin state in a mononuclear Iron(II) complex and high-temperature cooperative spin crossover mediated by hydrogen bonding. CHEMISTRY-A EUROPEAN JOURNAL, 22(1), 331–339.
Chicago author-date
Zheng, Sipeng, Niels RM Reintjens, Maxime A Siegler, Olivier Roubeau, Elisabeth Bouwman, Andrii Rudavskyi, Remco Havenith, and Sylvestre Bonnet. 2016. “Stabilization of the Low-spin State in a Mononuclear Iron(II) Complex and High-temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding.” Chemistry-a European Journal 22 (1): 331–339.
Chicago author-date (all authors)
Zheng, Sipeng, Niels RM Reintjens, Maxime A Siegler, Olivier Roubeau, Elisabeth Bouwman, Andrii Rudavskyi, Remco Havenith, and Sylvestre Bonnet. 2016. “Stabilization of the Low-spin State in a Mononuclear Iron(II) Complex and High-temperature Cooperative Spin Crossover Mediated by Hydrogen Bonding.” Chemistry-a European Journal 22 (1): 331–339.
Vancouver
1.
Zheng S, Reintjens NR, Siegler MA, Roubeau O, Bouwman E, Rudavskyi A, et al. Stabilization of the low-spin state in a mononuclear Iron(II) complex and high-temperature cooperative spin crossover mediated by hydrogen bonding. CHEMISTRY-A EUROPEAN JOURNAL. 2016;22(1):331–9.
IEEE
[1]
S. Zheng et al., “Stabilization of the low-spin state in a mononuclear Iron(II) complex and high-temperature cooperative spin crossover mediated by hydrogen bonding,” CHEMISTRY-A EUROPEAN JOURNAL, vol. 22, no. 1, pp. 331–339, 2016.
@article{8549878,
  abstract     = {The tetrapyridyl ligand bbpya (bbpya=N,N-bis(2,2'-bipyrid-6-yl)amine) and its mononuclear coordination compound [Fe(bbpya)(NCS)(2)] (1) were prepared. According to magnetic susceptibility, differential scanning calorimetry fitted to Sorai's domain model, and powder X-ray diffraction measurements, 1 is low-spin at room temperature, and it exhibits spin crossover (SCO) at an exceptionally high transition temperature of T-1/2=418 K. Although the SCO of compound 1 spans a temperature range of more than 150 K, it is characterized by a wide (21 K) and dissymmetric hysteresis cycle, which suggests cooperativity. The crystal structure of the LS phase of compound 1 shows strong N-H center dot center dot center dot S intermolecular H-bonding interactions that explain, at least in part, the cooperative SCO behavior observed for complex 1. DFT and CASPT2 calculations under vacuum demonstrate that the bbpya ligand generates a stronger ligand field around the iron(II) core than its analogue bapbpy (N,N'-di(pyrid-2yl)-2,2'-bipyridine-6,6'-diamine); this stabilizes the LS state and destabilizes the HS state in 1 compared with [Fe(bapbpy)( NCS)(2)] (2). Periodic DFT calculations suggest that crystal-packing effects are significant for compound 2, in which they destabilize the HS state by about 1500 cm(-1). The much lower transition temperature found for the SCO of 2 compared to 1 appears to be due to the combined effects of the different ligand field strengths and crystal packing.},
  author       = {Zheng, Sipeng and Reintjens, Niels RM and Siegler, Maxime A and Roubeau, Olivier and Bouwman, Elisabeth and Rudavskyi, Andrii and Havenith, Remco and Bonnet, Sylvestre},
  issn         = {0947-6539},
  journal      = {CHEMISTRY-A EUROPEAN JOURNAL},
  keywords     = {WIDE THERMAL HYSTERESIS,ROOM-TEMPERATURE,TRANSITION-TEMPERATURE,PERFORMANCE,VALIDATION,CHEMISTRY,INTERPLAY,POLYMERS,LIGANDS,SYSTEMS,cooperative effects,hydrogen bonds,iron,ligand design,spin crossover},
  language     = {eng},
  number       = {1},
  pages        = {331--339},
  title        = {Stabilization of the low-spin state in a mononuclear Iron(II) complex and high-temperature cooperative spin crossover mediated by hydrogen bonding},
  url          = {http://dx.doi.org/10.1002/chem.201503119},
  volume       = {22},
  year         = {2016},
}

Altmetric
View in Altmetric
Web of Science
Times cited: