TY - JOUR
T1 - Tuning of spin-crossover behavior in two cyano-bridged mixed-valence Fe III 2 FeIItrinuclear complexes based on a TpRligand
AU - Sulaiman, Arshia
AU - Jiang, Yi Zhan
AU - Javed, Mohammad Khurram
AU - Wu, Shu Qi
AU - Li, Zhao Yang
AU - Bu, Xian He
N1 - Funding Information:
This work was supported by the National Natural Science Foundation of China (NSFC, 21971124 and 22035003).
Publisher Copyright:
© the Partner Organisations.
PY - 2022/1/21
Y1 - 2022/1/21
N2 - Spin-crossover (SCO) complexes have been extensively studied in the past few decades owing to their bistable nature which find application in a myriad of areas. In order to enhance and optimize the SCO behavior, considerable attention is being paid towards the synthesis of discrete multinuclear spin-crossover complex systems. Here, two mixed-valence FeIII2FeII trinuclear complexes of the formula {[FeII(TPMA)][FeIII(TpR)(CN)3]2}·MeOH·2H2O (1) and {[FeII(TPMA)][FeIII(TpR)(CN)3]2}·H2O (2) [where TPMA = tris(2-pyridylmethyl)amine, Tp = tris(pyrazol-1-yl)borate, R = 3,5-dimethyl for 1 and H for 2] were synthesized and characterized. Magnetic measurements confirmed that complex 1 undergoes SCO at a high temperature (T1/2 = 410 K for the fresh sample and T1/2 = 406 K for the dried sample), while complex 2 displays near room temperature SCO (T1/2 = 283 K for the fresh sample and T1/2(↑) = 283 K and T1/2(↓) = 257 K for the dried sample). To the best of our knowledge, complex 1 has the highest transition temperature reported among trinuclear SCO complexes so far, which is a remarkable feature of multinuclear materials. Slight structural modifications tend to upend the SCO behavior which paves the way for fine tuning SCO.
AB - Spin-crossover (SCO) complexes have been extensively studied in the past few decades owing to their bistable nature which find application in a myriad of areas. In order to enhance and optimize the SCO behavior, considerable attention is being paid towards the synthesis of discrete multinuclear spin-crossover complex systems. Here, two mixed-valence FeIII2FeII trinuclear complexes of the formula {[FeII(TPMA)][FeIII(TpR)(CN)3]2}·MeOH·2H2O (1) and {[FeII(TPMA)][FeIII(TpR)(CN)3]2}·H2O (2) [where TPMA = tris(2-pyridylmethyl)amine, Tp = tris(pyrazol-1-yl)borate, R = 3,5-dimethyl for 1 and H for 2] were synthesized and characterized. Magnetic measurements confirmed that complex 1 undergoes SCO at a high temperature (T1/2 = 410 K for the fresh sample and T1/2 = 406 K for the dried sample), while complex 2 displays near room temperature SCO (T1/2 = 283 K for the fresh sample and T1/2(↑) = 283 K and T1/2(↓) = 257 K for the dried sample). To the best of our knowledge, complex 1 has the highest transition temperature reported among trinuclear SCO complexes so far, which is a remarkable feature of multinuclear materials. Slight structural modifications tend to upend the SCO behavior which paves the way for fine tuning SCO.
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U2 - 10.1039/d1qi01086g
DO - 10.1039/d1qi01086g
M3 - Article
AN - SCOPUS:85123936297
SN - 2052-1545
VL - 9
SP - 241
EP - 248
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
IS - 2
ER -