MCD spectroscopy of hexanuclear Mn(III) salicylaldoxime single-molecule magnets.

MCD spectroscopy of hexanuclear Mn(III) salicylaldoxime single-molecule magnets.
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六核 Mn(III) 水杨醛肟单分子磁体的 MCD 光谱。

DOI:
10.1039/c0dt00634c
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发表时间:
2010
期刊:
2003)
影响因子:
--
通讯作者:
Bradley JM
Bradley JM
中科院分区:
--
文献类型:
--
作者:
Bradley JM

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六核笼[Mn 6 O2(R-sao)6L 2(EtOH)x(H2O)y]“Mn 6”在低于特征阻断温度时表现为单分子磁体(SMM)。与[Mn 12 O 12(O2 CR)16(H2O)4]“Mn 12”一样,电子吸收光谱相当无特征,几乎没有关于磁性离子电子结构的信息。低温磁圆二色性(MCD)光谱提供了更高的分辨率的光学跃迁,也探测系统的磁性。Mn 6笼的基态自旋和阻塞温度都由通用Mn 6 O2核心的微妙结构扰动决定。报道了[Mn_6O_2(Et-sao)_6 {O_2CPh(Me)_2}_2(EtOH)_6](1)、[Mn_6O_2(Et-sao)_6 {O_2CPh}_2(EtOH)_4(H_2O)_2](2)、[Mn_6O_2(sao)_6 {O_2CPh}_2(EtOH)_4]·EtOH(3)和浇铸成聚合物膜的三核前体[Mn_3O(Et-sao)_3(MeOH)_3](ClO_4)(4)的吸光度和MCD光谱。SMM行为先前已被观察到使用粉末和单晶样品的磁化率测量。在(1)和(2)中,磁性离子的配位场环境被假定为是相似的,并且它们的不同阻断温度归因于有效交换常数的大小。(1)和(2)的MCD谱(其中基态自旋S = 12)表明Mn离子的配位场环境几乎相同,并且当去除晶体堆积力时,对于孤立分子,磁滞仍然存在。(1)和(2)之间的细微结构差异表现在不同波长下MCD响应的场依赖性,反映了带偏振的变化。(3)的MCD谱包含在(1)和(2)的MCD谱中不明显的特征。这些归因于5-配位Mn(III),其在所研究的化合物中是(3)所特有的。(3)具有基态自旋S = 4,较低的阻断温度,因此在MCD中没有可观察到的滞后,低至1.7 K。将(1)-(3)的MCD谱与(4)的MCD谱进行比较,证实了当这些材料浇铸成聚合物膜时Mn 6 O2核的完整性。
The hexanuclear cages [Mn6O2(R-sao)6L2(EtOH)x(H2O)y] “Mn6” behave as single-molecule magnets (SMMs) below a characteristic blocking temperature. As with [Mn12O12(O2CR)16(H2O)4] “Mn12” the electronic absorption spectra are rather featureless, yielding little information on the electronic structure of the magnetic ions. Low temperature Magnetic Circular Dichroism (MCD) spectra afford greater resolution of the optical transitions and also probe the magnetic properties of the system. Both the ground state spin and blocking temperature of the Mn6 cages are determined by subtle structural perturbations of a generic Mn6O2 core. Absorbance and MCD spectra are reported for [Mn6O2(Et-sao)6{O2CPh(Me)2}2(EtOH)6] (1), [Mn6O2(Et-sao)6{O2CPh}2(EtOH)4(H2O)2] (2), [Mn6O2(sao)6{O2CPh}2(EtOH)4]·EtOH (3) and the trinuclear precursor [Mn3O(Et-sao)3(MeOH)3](ClO4) (4) cast into polymer film. SMM behaviour has previously been observed using magnetic susceptibility measurements on powder and single-crystal samples. The ligand field environment of the magnetic ions is assumed to be similar in (1) and (2) and their different blocking temperatures are attributed to the magnitude of the effective exchange constant. The MCD spectra of (1) and (2), in which the ground state spin S = 12, show that the ligand field environments of the Mn ions are almost identical and that magnetic hysteresis persists for isolated molecules when crystal packing forces are removed. The subtle structural differences between (1) and (2) are manifested in the field dependence of the MCD response at different wavelengths that reflect changes in band polarisation. The MCD spectrum of (3) contains features not apparent in those of (1) and (2). These are attributed to 5-coordinate Mn(III), which is unique to (3) among the compounds studied. (3) has ground state spin S = 4, a lower blocking temperature and consequently no observable hysteresis in the MCD down to 1.7 K. Comparison of the MCD spectra of (1)–(3) to that of (4) confirms the integrity of the Mn6O2 core when these materials are cast into polymer film.
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