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A chromium(III) bis-acetylide complex containing a trans-diethyl-ethylenedithio-substituted tetrathiafulvalene (TTF) derivative: synthesis, crystal structures, and magnetic properties
Transition Metal Chemistry ( IF 1.6 ) Pub Date : 2021-03-25 , DOI: 10.1007/s11243-021-00453-9
Junichi Nishijo , Masato Uchida , Masaya Enomoto , Motoko Akita

A new Cr(III) bis-acetylide complex containing redox-active ethynyl-substituted 4-methyl-4′,5′-trans-diethyl-ethylenedithio-tetrathiafulvalene, [Cr(III)cyclam(C≡C-MeEt2EDT-TTF)2]n+ ([1]n+) was synthesized. The crystal structures of two salts, [1][Ni(dmit)2] (dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate) and [1][Ni(mnt)2]3 (mnt = maleonitriledithiolate), were determined by single-crystal X-ray diffraction. In the crystal of [1][Ni(dmit)2], the trans-diethyl group of [1]+ is in the axial position and prevents π-stacking of the TTF units, resulting in a negligibly weak spin–spin interaction between Cr3+ and [Ni(dmit)2]. In contrast, in [1][Ni(mnt)2]3, the trans-diethyl group is in the equatorial position in [1][Ni(mnt)2]3 owing to the strong attractive force between the π-stacked TTF+ units and the [Ni(mnt)2] anions. This π-stacking has a significant effect on the magnetic property of [1] [Ni(mnt)2]3. The π-stacked TTF+ units and [Ni(mnt)2] anions behave approximately as a one-dimensional S = 1/2 antiferromagnetic chain connecting the spins of Cr3+ antiferromagnetically.



中文翻译:

含反式二乙基-乙撑二硫代四硫富富瓦烯(TTF)衍生物的铬(III)双乙炔化物配合物:合成,晶体结构和磁性

新的CR(III)双-乙炔化物络合物含有氧化还原活性乙炔基取代的4-甲基-4',5'-反式-二亚乙二硫基硫富瓦烯,[铬(III)cyclam(C≡C-满足2 EDT-合成了TTF)2 ] n +([ 1 ] n +)。两种盐的晶体结构,[ 1 ] [Ni(dmit)2 ](dmit = 2-thioxo-1,3-dithiole-4,5-dithiolate)和[ 1 ] [Ni(mnt)2 ] 3(mnt通过单晶X射线衍射测定。在[ 1 ] [Ni(dmit)2 ]的晶体中,[ 1 ] +的反式二乙基处于轴向位置并阻止TTF单元的π堆积,从而导致Cr 3+和[Ni(dmit)2 ] -之间的自旋-自旋相互作用微不足道。相反,在[ 1 ] [Ni(mnt)2 ] 3中,由于π堆积的TTF之间的强吸引力反式二乙基在[ 1 ] [Ni(mnt)2 ] 3中处于赤道位置。+单位和[Ni(mnt)2 ] -阴离子。该π堆积对[ 1 ] [Ni(mnt)2 ] 3的磁性能具有显着影响。π堆叠的TTF+单位和[Ni(mnt)2 ] -阴离子的行为近似为一维S  = 1/2反铁磁链,通过反铁磁连接Cr 3+的自旋。

更新日期:2021-03-26
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