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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 |
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| Authors: | Nishijo Junichi Uchida Masato Enomoto Masaya Akita Motoko |
| Institution: | 1.Graduate School of Science and Engineering, Meisei University, 2-1-1 Hodokubo, Hino, Tokyo, 191-8506, Japan ;2.Department of Chemistry, Faculty of Science Division I, Tokyo University of Science, Kagurazqaka 1–3, Shinjuku-ku, Tokyo, 162-8601, Japan ;3.Graduate School of Material Science, Josai University, 1-1 Keyakidai, Sakado-shi, Saitama, 350-0295, Japan ; |
| Abstract: | 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. |
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