Fine-tuning of thermally induced SCO behaviors of trinuclear cyanido-bridged complexes by regulating the electron donating ability of CCN-terminal fragments
To achieve fine regulation of FeII SCO behavior, a series of trinuclear cyanido-bridged complexes trans-[CpMen(dppe)MII(CN)]2[Fe1II(abpt)2](OTf)2 (1-4) (1, M = Fe2 and n = 1; 2, M = Fe2 and n = 4; 3, M = Fe2 and n = 5; 4, M = Ru and n = 5; CpMen = alkyl cyclopentadienyl with n = 1, 4, 5; dppe = 1,2-bis-(diphenylphosphino)ethane; abpt = 4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole and OTf = CF3SO3-) were synthesized and fully characterized by using elemental analysis, X-ray crystallography, magnetic measurements, variable-temperature IR spectroscopy and Mössbauer spectroscopy. It is worth mentioning that different from many mononuclear Fe(abpt)2X2 (X = NCS, NCSe, N(CN)2, C(CN)3, (NC)2CC(OCH3)C(CN)2, (NC)2CC(OC2H5)C(CN)2, C16SO3 and Cl) complexes with more than one polymorph, only one polycrystalline form was found in complexes 1-4. Moreover, the thermally induced SCO behaviors of these four complexes are independent of intermolecular π-π interactions. The electron-donating ability of the CCN-terminal fragment of CpMen(dppe)MIICN can be flexibly regulated by changing the methyl number (n) of the cyclopentadiene ligand or metal ion type (MII). These investigations indicate that the electron-donating ability of the CCN-terminal fragment has an influence on the SCO behavior of Fe1II. The spin transition temperature (T1/2) of the complexes decreases with the increase of the electron-donating ability of the fragment CpMen(dppe)MII. This study provides a new strategy to predict and precisely regulate the behaviors of SCO complexes.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:53 |
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| Enthalten in: |
Dalton transactions (Cambridge, England : 2003) - 53(2024), 8 vom: 20. Feb., Seite 3777-3784 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Huang, Ying-Ying [VerfasserIn] |
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| Anmerkungen: |
Date Revised 20.02.2024 published: Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1039/d3dt04226j |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM367943794 |
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| 100 | 1 | |a Huang, Ying-Ying |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Fine-tuning of thermally induced SCO behaviors of trinuclear cyanido-bridged complexes by regulating the electron donating ability of CCN-terminal fragments |
| 264 | 1 | |c 2024 | |
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| 500 | |a Date Revised 20.02.2024 | ||
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| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a To achieve fine regulation of FeII SCO behavior, a series of trinuclear cyanido-bridged complexes trans-[CpMen(dppe)MII(CN)]2[Fe1II(abpt)2](OTf)2 (1-4) (1, M = Fe2 and n = 1; 2, M = Fe2 and n = 4; 3, M = Fe2 and n = 5; 4, M = Ru and n = 5; CpMen = alkyl cyclopentadienyl with n = 1, 4, 5; dppe = 1,2-bis-(diphenylphosphino)ethane; abpt = 4-amino-3,5-bis-(pyridin-2-yl)-1,2,4-triazole and OTf = CF3SO3-) were synthesized and fully characterized by using elemental analysis, X-ray crystallography, magnetic measurements, variable-temperature IR spectroscopy and Mössbauer spectroscopy. It is worth mentioning that different from many mononuclear Fe(abpt)2X2 (X = NCS, NCSe, N(CN)2, C(CN)3, (NC)2CC(OCH3)C(CN)2, (NC)2CC(OC2H5)C(CN)2, C16SO3 and Cl) complexes with more than one polymorph, only one polycrystalline form was found in complexes 1-4. Moreover, the thermally induced SCO behaviors of these four complexes are independent of intermolecular π-π interactions. The electron-donating ability of the CCN-terminal fragment of CpMen(dppe)MIICN can be flexibly regulated by changing the methyl number (n) of the cyclopentadiene ligand or metal ion type (MII). These investigations indicate that the electron-donating ability of the CCN-terminal fragment has an influence on the SCO behavior of Fe1II. The spin transition temperature (T1/2) of the complexes decreases with the increase of the electron-donating ability of the fragment CpMen(dppe)MII. This study provides a new strategy to predict and precisely regulate the behaviors of SCO complexes | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a He, Yong |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Yang |e verfasserin |4 aut | |
| 700 | 1 | |a Fu, Jin-Hui |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Xiao-Lin |e verfasserin |4 aut | |
| 700 | 1 | |a Wu, Xin-Tao |e verfasserin |4 aut | |
| 700 | 1 | |a Sheng, Tian-Lu |e verfasserin |4 aut | |
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| 773 | 1 | 8 | |g volume:53 |g year:2024 |g number:8 |g day:20 |g month:02 |g pages:3777-3784 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1039/d3dt04226j |3 Volltext |
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