Correlation between Supramolecular Connectivity and Magnetic Behaviour of [FeIII(5-X-qsal)2]+-Based Salts Prone to Exhibit SCO Transition

We present an extensive study to determine the relationship between structural features of spin crossover (SCO) systems based on N-(8-quinolyl)salicylaldimine (qsal) ligand derivatives and their magnetic properties. Thirteen new compounds with general formula [FeIII(5-X-qsal)2]+ (X = H, F, Cl, Br an...

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Vydáno v:Magnetochemistry Ročník 8; číslo 1; s. 1
Hlavní autoři: Vieira, Bruno J. C., Pereira, Laura C. J., Gama, Vasco da, Santos, Isabel C., Cerdeira, Ana C., Waerenborgh, João C.
Médium: Journal Article
Jazyk:angličtina
Vydáno: Basel MDPI AG 01.01.2022
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ISSN:2312-7481, 2312-7481
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Abstract We present an extensive study to determine the relationship between structural features of spin crossover (SCO) systems based on N-(8-quinolyl)salicylaldimine (qsal) ligand derivatives and their magnetic properties. Thirteen new compounds with general formula [FeIII(5-X-qsal)2]+ (X = H, F, Cl, Br and I) coupled to Cl−, ClO4−, SCN−, PF6−, BF4− and BPh4− anions were prepared and magnetically characterized. The structure/properties correlations observed in these compounds were compared to those of salts with the same [FeIII(qsal-X)2]+ cations previously reported in the literature. These cations favour the LS configuration in compounds with the weakest connectivity. As connectivity increases most of them present HS states at room temperature and structures may be described as arrangements of parallel layers of interacting cation dimers. All the compounds based on these cations undergoing complete SCO transitions within the 4–300 K temperature range have high intralayer connectivity. If, however, the interlayer connectivity becomes very strong they remain blocked in the HS or in the LS state. The SCO transition may be affected by the slightest change of solvent molecules content, disorder or even crystallinity of the sample and it remain difficult to predict which kind of ligand substituent should be selected to obtain compounds with the desired connectivity.
AbstractList We present an extensive study to determine the relationship between structural features of spin crossover (SCO) systems based on N-(8-quinolyl)salicylaldimine (qsal) ligand derivatives and their magnetic properties. Thirteen new compounds with general formula [FeIII(5-X-qsal)2]+ (X = H, F, Cl, Br and I) coupled to Cl−, ClO4−, SCN−, PF6−, BF4− and BPh4− anions were prepared and magnetically characterized. The structure/properties correlations observed in these compounds were compared to those of salts with the same [FeIII(qsal-X)2]+ cations previously reported in the literature. These cations favour the LS configuration in compounds with the weakest connectivity. As connectivity increases most of them present HS states at room temperature and structures may be described as arrangements of parallel layers of interacting cation dimers. All the compounds based on these cations undergoing complete SCO transitions within the 4–300 K temperature range have high intralayer connectivity. If, however, the interlayer connectivity becomes very strong they remain blocked in the HS or in the LS state. The SCO transition may be affected by the slightest change of solvent molecules content, disorder or even crystallinity of the sample and it remain difficult to predict which kind of ligand substituent should be selected to obtain compounds with the desired connectivity.
Author Santos, Isabel C.
Pereira, Laura C. J.
Waerenborgh, João C.
Cerdeira, Ana C.
Vieira, Bruno J. C.
Gama, Vasco da
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SubjectTerms Behavior
Cations
Dimers
Fe (III)
Hydrogen bonds
Interlayers
Ligands
Magnetic properties
Room temperature
Schiff base ligands
spin crossover
supramolecular chemistry
Temperature
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Title Correlation between Supramolecular Connectivity and Magnetic Behaviour of [FeIII(5-X-qsal)2]+-Based Salts Prone to Exhibit SCO Transition
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