Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 60, Issue 7, Pages 3515-3518Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202013374
Keywords
iron; magnetic properties; molecular materials; nanohoop ligand; spin crossover
Categories
Funding
- EPSRC [EP/M022064/2]
- ERC [CoG 646740]
- Spanish MICINN [RYC2018-024692-I]
- Spanish Structures of Excellence Maria de Maeztu program [MDM-2017-0767]
- National Science Foundation [CHE-1800586]
- Friedrich-Alexander-University Erlangen-Nurnberg (FAU)
- EPSRC [EP/M022064/2] Funding Source: UKRI
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The addition of bipyridyl-embedded cycloparaphenylene nanohoop to an iron(II) complex leads to a distorted octahedral structure with spin-crossover behavior. Computational studies suggest that the size and curvature of the nanohoop play a critical role in determining the SCO properties of the iron(II) complex.
Addition of the bipyridyl-embedded cycloparaphenylene nanohoop bipy[9]CPP to [Fe{H2B(pyz)(2)}] (pyz=pyrazolyl) produces the distorted octahedral complex [Fe(bipy[9]CPP){H2B(pyz)(2)}(2)] (1). The molecular structure of 1 shows that the nanohoop ligand contains a non-planar bipy unit. Magnetic susceptibility measurements indicate spin-crossover (SCO) behaviour with a T-1/2 of 130 K, lower than that of 160 K observed with the related compound [Fe(bipy){H2B(pyz)(2)}(2)] (2), which contains a conventional bipy ligand. A computational study of 1 and 2 reveals that the curvature of the nanohoop leads to the different SCO properties, suggesting that the SCO behaviour of iron(II) can be tuned by varying the size and diameter of the nanohoop.
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