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:
影响因子:
--
通讯作者:
Bradley JM
中科院分区:
文献类型:
--
作者:
Bradley JM
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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DOI:
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发表时间:
1994
期刊:
影响因子:
--
作者:
J. Villain;F. Hartman;R. Sessoli;A. Rettori
通讯作者:
A. Rettori
影响因子:
4.6
作者:
R. Saalfrank;A. Scheurer;R. Prakash;F. Heinemann;Takayuki Nakajima;F. Hampel;R. Leppin;B. Pilawa;Holger Rupp;P. Müller
通讯作者:
R. Saalfrank;A. Scheurer;R. Prakash;F. Heinemann;Takayuki Nakajima;F. Hampel;R. Leppin;B. Pilawa;Holger Rupp;P. Müller
影响因子:
--
作者:
A. Sieber;R. Bircher;O. Waldmann;G. Carver;G. Chaboussant;H. Mutka;H. Güdel
通讯作者:
H. Güdel
DOI:
--
发表时间:
1998
期刊:
影响因子:
--
作者:
A. Würger
通讯作者:
A. Würger
影响因子:
--
作者:
K. Awaga;Yoshihito Suzuki;H. Hachisuka;K. Takeda
通讯作者:
K. Awaga;Yoshihito Suzuki;H. Hachisuka;K. Takeda