Acid and alkali-resistant Dy-4 coordination clusters: synthesis, structure and slow magnetic relaxation behaviors
Acid and alkali-resistant Dy-4 coordination clusters: synthesis, structure and slow magnetic relaxation behaviors
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耐酸碱Dy4配位簇：合成、结构和慢磁弛豫行为
DOI：
10.1039/d0tc03250f
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发表时间：
2021
影响因子：
6.4
通讯作者：
Liang Fupei
中科院分区：
文献类型：
--
作者：
Yu Shui;Hu Huancheng;Chen Yunkai;Chen Zilu;Zhang Zhanyun;Ding Man-Man;Zhang Yi-Quan;Liu Dongcheng;Liang Yuning;Liang Fupei
两个新的基于[Dy4]的配位簇[Dy4(L1)2(L2)4(NO3)2(EtOH)4]·2MeOH (1) (H3L1 = 2-(β-萘氨基)-2-(羟甲基)-1-丙醇，HL2 = 2-羟基-1-萘醛)和合成并表征了分别具有平面和蝴蝶状骨架的[Dy4(μ4-O)(HL3)4(H2L3)2]·3H2O·EtOH·CH3CN (2) (H3L3 = 3-(((2-羟基萘-1-基)亚甲基)氨基)-丙烷-1,2-二醇)。这表明，1 是场感应单分子磁体，在 800 Oe 的直流磁场下，其有效势垒为 Ueff = 6.1 K，而 2 在零直流磁场下，显示出慢磁弛豫行为，Ueff = 2.6 K。采用磁稀释法进一步研究1和2的磁弛豫行为；结果，1和2的慢磁弛豫行为主要归因于单个Dy3+离子，从头算的结果也证实了这一点。有趣的是，它们在水和常见有机溶剂以及较宽pH范围（2.5-14）的酸碱溶液中都具有优异的稳定性。令人惊讶的是，2即使在18 M NaOH水溶液中也很稳定，这在0D配位化合物中很少报道，是顺磁性金属团簇稳定性的突破。它有助于开发化学稳定的单分子磁体，用于潮湿和酸性/碱性介质中的应用。
Two new [Dy4]-based coordination clusters [Dy4(L1)2(L2)4(NO3)2(EtOH)4]·2MeOH (1) (H3L1 = 2-(β-naphthalideneamino)-2-(hydroxylmethyl)-1-propanol, HL2 = 2-hydroxy-1-naphthaldehyde) and [Dy4(μ4-O)(HL3)4(H2L3)2]·3H2O·EtOH·CH3CN (2) (H3L3 = 3-(((2-hydroxynaphthaen-1-yl)methylene)amino)-propane-1,2-diol) with planar and butterfly-like skeletons, respectively, were synthesized and characterized. This revealed that 1 is a field-induced single-molecule magnet with an effective barrier of Ueff = 6.1 K under a dc field of 800 Oe and 2 shows slow magnetic relaxation behaviour with Ueff = 2.6 K under zero dc field. The magnetic dilution method was applied to further investigate the magnetic relaxation behaviors of 1 and 2; as a result, slow magnetic relaxation behaviors of 1 and 2 were mostly attributed to the single Dy3+ ions, which was also confirmed by the result of ab initio calculation. Interestingly, both of them possess excellent stability in water and common organic solvents, as well as in acid and base solutions with a wide pH range (2.5–14). Surprisingly, 2 is stable even in 18 M NaOH aqueous solutions, which is rarely reported in 0D coordination compounds and is a breakthrough for paramagnetic metal clusters in stability. It helps to develop chemically stable single-molecule magnets for their application in moisture and acidic/alkaline media.