Electric transport properties of Mn<sub>12</sub>-acetate films measured with self-assembling tunnelling junction

Ma, Lian; Chen, Chi; Agnolet, Glenn; Nie, Jia-Cai; Zhao, Huaiqing; Dunbar, Kim R.

doi:10.1088/0022-3727/42/9/095104

Cited by 3 publications

(3 citation statements)

References 55 publications

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“…Elemental analysis: Anal. calcd for C 71 H 120 O 28 Ru 6 N 2 : C,41.97;H,5.88;N,1.36. Found: C,42.77;H,6.02;N,1.56. Note: As the yield of the reaction was significantly low, we eluted further and identified that various other products are also formed in the reaction.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…calcd for C 71 H 120 O 28 Ru 6 N 2 : C,41.97;H,5.88;N,1.36. Found: C,42.77;H,6.02;N,1.56. Note: As the yield of the reaction was significantly low, we eluted further and identified that various other products are also formed in the reaction. For example, the second fraction of the column is identified as a hexanuclear cluster with the molecular formula of [Ru 6 III (O) 2 (μ-OH) 2 (t-BuCO 2 ) 12 (pyridine) 2 ] (4, yield = 5%) which was reported by us earlier, 14b and the third major fraction from the column is an oxo-centered Ru(III) triangle with the general molecular formula [Ru 3 (O)(t-BuCO 2 ) 6 (pyridine) 3 ] + (m/z = 1164.15 g/mol; yield = 37.1%; vide inf ra).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

et al. 2018

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Three structurally analogous hexanuclear ruthenium(III) complexes were isolated with the general molecular formula of [Ru6 III(O)2(μ4-η2-η2-CH2O2)(t-BuCO2)12(L)2] where L = pyridine (1) or 4-dimethylamino pyridine (DMAP; 2) or 4-cyanopyridine (3). Complexes 1 and 3 were solved in the tetragonal I4̅c2 and P4 1212 space group, respectively, while 2 crystallized in the monoclinic system with P2 1 /c space group. In all three complexes, two oxo-centered Ru(III) triangles were bridged by a unique and a rare methylenediolate (CH2O2)2–) ligand. This (CH2O2)2– group is reported to be an intermediate, which is not isolated in its metal-free form, to date, as it is unstable. Control experiments performed evidently reveal that the unique reaction condition followed is mandatory to isolate 1–3 and the origin of (CH2O2)2– is unknown at the moment, as no precursor was used to form this intermediate. The presence of (CH2O2)2– identified through X-ray diffraction was further unambiguously confirmed by various 1D (1H and 13C) and 2D-NMR (HSQC, TOCSY, NOESY, and DEPT) spectroscopies. Direct current (dc) magnetic susceptibility measurements performed on 1 and 2 reveal the predominant antiferromagnetic exchange interaction between the Ru(III) centers result in a diamagnetic ground state at 2.0 K. The paramagnetic influence of 1–3 at room temperature evidently felt by the 1H nuclei of the (CH2O2)2– unit predominates compared to other NMR active nuclei in the complexes. The presence of an electron donating or withdrawing substituent on the terminal pyridine results in significant change in the dihedral angle of two oxo-centered triangular (Ru3O−) planes. The change in the structural parameters of 1–3 due to the substituents markedly reflected on the absorption profile and redox behavior, which are systematically investigated. Preliminary galvanostatic charge/discharge cycling experiments performed on a representative complex (3) suggest that 3 can be a promising candidate to employ as an effective multiple electron charge carrier in a nonaqueous redox flow battery.

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Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

et al. 2018

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“…In the last few decades, molecular materials have been proposed as plausible alternatives for the miniaturization of components for information storage devices. [1][2][3][4][5] Molecules represent the well-defined minimum size limit, [6][7][8][9][10] along with additional advantages when compared with the more common top-down approach: solid state materials typically lose their bulk properties at the nanoscale. [11][12][13] Molecule-based alternatives to optical, 14,15 electric 16,17 or magnetic 18,19 materials have been studied with excellent perspectives, including multifunctional materials exhibiting tailor-made combinations of the abovementioned materials.…”

Section: Introductionmentioning

confidence: 99%

Tuning the spin crossover behavior of the polyanion [(H₂O)₆Fe₃(μ-L)₆]^6–: the case of the cesium salt

et al. 2018

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The magnetic behavior of the polyanion [Fe3(μ-L)6(H2O)6]6- (L2- = (1,2,4-triazol-4-yl)ethanedisulfonate) as the corresponding dimethylammonium salt shows memory effect above room temperature, with a dynamic thermal hysteresis cycle over 90 K and temperature-induced excited spin state trapping (TIESST) phenomena at the highest temperatures reported. Taking advantage of the polyanionic nature of this trimetallic complex, we were able to substitute the dimethylammonium cations by the monovalent heavy alkali metal cesium. This methathesis yielded the salt Cs6[Fe3(μ-L)6(H2O)6], with different molecular packing that increases the number and strength of cation-anion interactions, including a more robust H-bonded network. In this phase, the spin transition still occurs above room temperature, but it is more abrupt and narrow (≈50 K wide hysteresis). Despite these differences, TIESST is observed with almost identical characteristic temperature (TTIESST = 240 K) than in the parent compound, which is an additional experimental evidence supporting the molecular origin of the TIESST behavior in these materials.

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Detection of the intrinsic two energy gaps in individual Mn12 single molecule magnets

Meng¹,

Lin²,

Yang³

et al. 2012

Chemical Physics Letters

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Electric transport properties of Mn₁₂-acetate films measured with self-assembling tunnelling junction

Cited by 3 publications

References 55 publications

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

Tuning the spin crossover behavior of the polyanion [(H₂O)₆Fe₃(μ-L)₆]^6–: the case of the cesium salt

Detection of the intrinsic two energy gaps in individual Mn12 single molecule magnets

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Electric transport properties of Mn12-acetate films measured with self-assembling tunnelling junction

Cited by 3 publications

References 55 publications

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

Unusual Methylenediolate Bridged Hexanuclear Ruthenium(III) Complexes: Syntheses and Their Application

Tuning the spin crossover behavior of the polyanion [(H2O)6Fe3(μ-L)6]6–: the case of the cesium salt

Detection of the intrinsic two energy gaps in individual Mn12 single molecule magnets

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Product

Resources

About

Electric transport properties of Mn₁₂-acetate films measured with self-assembling tunnelling junction

Tuning the spin crossover behavior of the polyanion [(H₂O)₆Fe₃(μ-L)₆]^6–: the case of the cesium salt