Synthesis, structures and magnetic properties of heterobimetallic RuIII–3d (3d = Mn, Ni) compounds based on the chiral RuIII building block†,New Journal of Chemistry

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Synthesis, structures and magnetic properties of heterobimetallic RuIII–3d (3d = Mn, Ni) compounds based on the chiral RuIII building block†
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2018-08-31 00:00:00 , DOI: 10.1039/c8nj03747g
Jing Ru _{1,

2,

3,

4,

5} , Ru-Fen Zhang _{1,

2,

3,

4,

5} , Yang Shi _{1,

2,

3,

4,

5} , Shao-Liang Zhang _{1,

2,

3,

4,

5} , Qian-Li Li _{1,

2,

3,

4,

5} , Chun-Lin Ma _{1,

2,

3,

4,

5}

Affiliation

Two pairs of chiral cyano-bridged heterobimetallic compounds, [Mn(salen)Ru((R,R)-(5-Br-salcy))(CN)₂]_n (1), [Mn(salen)Ru((S,S)-(5-Br-salcy))(CN)₂]_n (2), [Ni(tren)][Ru((R,R)-(5-Cl-salcy))(CN)₂]₂ (3), and [Ni(tren)][Ru((S,S)-(5-Cl-salcy))(CN)₂]₂ (4) [salcy²⁻ = N,N′-(1,2-cyclohexanediylethylene) bis(salicylideneiminato) dianion, tren = tri(2-aminoethyl)amine], have been synthesized and characterized by elemental analysis, IR spectroscopy, X-ray diffraction analyses, and circular dichroism (CD) and vibrational circular dichroism (VCD) spectra. Single X-ray diffraction analysis reveals that complexes 1 and 2 possess a chiral 1D zigzag chain structure that consists of alternating (R,R/S,S)-trans-[Ru(5-Br-salcy)(CN)₂]⁻ and [Mn^III(salen)]⁺ units. Complexes 3 and 4 are trinuclear complexes in which the central Ni(II) ion is coordinated with two terminal (R,R/S,S)-trans-[Ru(5-Cl-salcy)(CN)₂]⁻ units through cyanide bridges. Investigation of magnetic susceptibilities indicates that antiferromagnetic coupling exists between the cyano-bridged Ru^III and Mn^III ions for complexes 1 and 2. An estimation of the barrier size (E_a) for 1 reveals a value of 19.1 K, with a characteristic time (τ₀) of 1.95 × 10⁻⁸. Moreover, complexes 3 and 4 exhibit ferromagnetic coupling between Ru^III and Ni^II through the cyanide bridges with J = 2.73 cm⁻¹.

中文翻译：

合成，结构和异核钌的磁特性^III -3D（3D =锰，镍）化合物基于手性钌上^III积木†

两对手性氰基桥联杂双金属化合物[Mn（salen）Ru（（R，R）-（5-Br-salcy））（CN）₂ ] _n（1），[Mn（salen）Ru（（S，S）-（5-Br-salcy））（CN）₂ ] _n（2），[Ni（tren）] [Ru（（R，R）-（5-Cl-salcy））（CN）₂ ] ₂（3）和[Ni（tren）] [Ru（（S，S）-（5-Cl-salcy））（CN）₂ ] ₂（4）[salcy ²⁻ = N，N已合成并通过元素分析，红外光谱，X射线衍射分析和圆二色性（CD）合成了'-（1,2-环己二乙烯）双（水杨基亚胺基）双阴离子，tren =三（2-氨基乙基）胺和振动圆二色性（VCD）光谱。单次X射线衍射分析显示，配合物1和2具有手性1D之字形链结构，该结构由交替的（R，R / S，S）-反-[Ru（5-Br-salcy）（CN）₂ ] ^-组成和[Mn ^III（salen）] ⁺单位。配合物3和4是三核络合物，其中中心Ni（II）离子通过氰化物桥与两个末端（R，R / S，S）-反式-[Ru（5-Cl-salcy）（CN）₂ ] ^-单元配位。磁化率的研究表明，配合物1和2在氰基桥联的Ru ^III和Mn ^III离子之间存在反铁磁耦合。阻挡大小（的估计Ë_一对）1揭示了19.1 K的值，具有特征时间（τ ₀）1.95×10 ^-8。此外，配合物3和4通过J＝ 2.73cm ^-1的氰化物桥表现出Ru ^III和Ni ^II之间的铁磁耦合。

更新日期：2018-08-31

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