Manipulating the spin crossover behavior in a series of {FeFeII} complexes
Three cyanide-bridged {Fe2Fe} complexes of formula {[(TpR)Fe(CN)3]2[Fe(bnbpen)]}·S (TpR = Tp for 1·S, Tp3-Me for 2·S, and Tp* for 3·S, respectively; bnbpen = N,N'-bis-(2-naphthylmethyl)-N,N'-bis(2-picolyl)-ethylenediamine) have been prepared and characterized here. Single-crystal X-ray diffraction analysis revealed that all compounds feature right angled trinuclear structures with two [(TpR)Fe(CN)3]- units at the ends and one [Fe(bnbpen)]2+ at the centre. Besides the rich hydrogen bonds, remarkable π-π interactions are evidenced in all compounds between the intermolecular naphthyl and pyrazolyl rings. As a result, compounds 1·S and 2·S exhibit irreversible two-step and one-step spin-transitions, respectively, during the process of removing solvents, with T1/2 at 314 K and 376 K for 1·S and 350 K for 2·S, while compound 3·S shows a reversible one-step spin transition at relatively lower temperatures with T1/2 = 250 K, and what's more, an irreversible small magnetic change accompanied by the loss of lattice solvents was observed. The solvent-free compounds show SCO properties at lower temperatures than the corresponding solvated ones; however, the solvent-free compound 1 maintains an unexpected high-spin state and does not follow the trend that their transition temperatures decrease with the enhancement of the electron donor properties of the TpR ligands (Tp* < Tp3-Me < Tp), likely due to the more compact π-π stacking mode in comparison with those for compounds 2·S and 3·S.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2020 |
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| Erschienen: |
2020 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:49 |
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| Enthalten in: |
Dalton transactions (Cambridge, England : 2003) - 49(2020), 18 vom: 14. Mai, Seite 5949-5956 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Chen, Jia-Tao [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Revised 12.05.2020 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1039/d0dt00016g |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM308992180 |
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| 041 | |a eng | ||
| 100 | 1 | |a Chen, Jia-Tao |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Manipulating the spin crossover behavior in a series of {FeFeII} complexes |
| 264 | 1 | |c 2020 | |
| 336 | |a Text |b txt |2 rdacontent | ||
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| 500 | |a Date Revised 12.05.2020 | ||
| 500 | |a published: Print-Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a Three cyanide-bridged {Fe2Fe} complexes of formula {[(TpR)Fe(CN)3]2[Fe(bnbpen)]}·S (TpR = Tp for 1·S, Tp3-Me for 2·S, and Tp* for 3·S, respectively; bnbpen = N,N'-bis-(2-naphthylmethyl)-N,N'-bis(2-picolyl)-ethylenediamine) have been prepared and characterized here. Single-crystal X-ray diffraction analysis revealed that all compounds feature right angled trinuclear structures with two [(TpR)Fe(CN)3]- units at the ends and one [Fe(bnbpen)]2+ at the centre. Besides the rich hydrogen bonds, remarkable π-π interactions are evidenced in all compounds between the intermolecular naphthyl and pyrazolyl rings. As a result, compounds 1·S and 2·S exhibit irreversible two-step and one-step spin-transitions, respectively, during the process of removing solvents, with T1/2 at 314 K and 376 K for 1·S and 350 K for 2·S, while compound 3·S shows a reversible one-step spin transition at relatively lower temperatures with T1/2 = 250 K, and what's more, an irreversible small magnetic change accompanied by the loss of lattice solvents was observed. The solvent-free compounds show SCO properties at lower temperatures than the corresponding solvated ones; however, the solvent-free compound 1 maintains an unexpected high-spin state and does not follow the trend that their transition temperatures decrease with the enhancement of the electron donor properties of the TpR ligands (Tp* < Tp3-Me < Tp), likely due to the more compact π-π stacking mode in comparison with those for compounds 2·S and 3·S | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Zhao, Xin-Hua |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Yuan-Zhu |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t Dalton transactions (Cambridge, England : 2003) |d 2004 |g 49(2020), 18 vom: 14. Mai, Seite 5949-5956 |w (DE-627)NLM149339739 |x 1477-9234 |7 nnns |
| 773 | 1 | 8 | |g volume:49 |g year:2020 |g number:18 |g day:14 |g month:05 |g pages:5949-5956 |
| 856 | 4 | 0 | |u http://dx.doi.org/10.1039/d0dt00016g |3 Volltext |
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