A chromium(III) bis-acetylide complex containing a trans-diethyl-ethylenedithio-substituted tetrathiafulvalene (TTF) derivative: synthesis, crystal structures, and magnetic properties


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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  1. 1.

    Maspoch D, Ruiz-Molina D, Wurst K, Domingo N, Cavallini M, Biscarini F, Tejada J, Rovira C, Veciana J (2003) A nanoporous molecular magnet with reversible solvent-induced mechanical and magnetic properties. Nature Mater 2:190–195

    CAS  Article  Google Scholar 

  2. 2.

    Ohba M, Yoneda K, Agustí G, Muñoz MC, Gaspar AB, Real JA, Yamasaki M, Ando H, Nakao Y, Sasaki S, Kitagawa S (2009) Bidirectional chemo-switching of spin state in a microporous framework. Angew Chem Int Ed 48:4767–4771

    CAS  Article  Google Scholar 

  3. 3.

    Nakaya M, Ohtani R, Hayami S (2020) Guest modulated spin states of metal complex assemblies. Eur J Inorg Chem 2020:3709–3719

    CAS  Article  Google Scholar 

  4. 4.

    Koumousi ES, Jeon I, Gao Q, Dechambenoit P, Woodruff DN, Merzeau P, Buisson L, Jia X, Li D, Volatron F, Mathonière C, Clérac R (2014) Metal-to-metal electron transfer in co/fe prussian blue molecular analogues: the ultimate miniaturization. J Am Chem Soc 136:15461–15464

    CAS  Article  Google Scholar 

  5. 5.

    Ishikawa M, Asari T, Matsuda M, Tajima H, Hanasaki N, Naito T, Inabe T (2010) Giant magnetoresistance response by the π–d interaction in an axially ligated phthalocyanine conductor with two-dimensional stacking structure. J Mater Chem 20:4432–4438

    CAS  Article  Google Scholar 

  6. 6.

    Komatsu H, Matsushita MM, Yamaura S, Sugawara Y, Suzuki K, Sugawara T (2010) Influence of magnetic field upon the conductance of a unicomponent crystal of a tetrathiafulvalene-based nitronyl nitroxide. J Am Chem Soc 132:4528–4529

    CAS  Article  Google Scholar 

  7. 7.

    Nishijo J, Miyazaki A, Enoki T, Watanabe R, Kuwatani Y, Iyoda M (2005) d-Electron-induced negative magnetoresistance of π-d interaction system based on brominated-ttf donor. Inorg Chem 44:2493–2506

    CAS  Article  Google Scholar 

  8. 8.

    Uji S, Shinagawa H, Terashima T, Yakabe T, Terai Y, Tokumoto M, Kobayashi A, Tanaka H, Kobayashi H (2001) Magnetic-field-induced superconductivity in a two-dimensional organic conductor. Nature 410:908–910

    CAS  Article  Google Scholar 

  9. 9.

    Coronado E (2020) Molecular magnetism: from chemical design to spin control in molecules, materials and devices. Nature Rev Mater 5:87–104

    Article  Google Scholar 

  10. 10.

    Preuss KE (2015) Metal-radical coordination complexes of thiazyl and selenazyl ligands. Coord Chem Rev 289–290:49–61

    Article  Google Scholar 

  11. 11.

    Shi JY, Chen YC, Wu MZ, Liu ZY (2019) Synthesis of a series of hetero-multi-spin Ln2Cu3 complexes based on a methyl-pyrazole nitronyl nitroxide radical with slow magnetic relaxation behaviors. Dalton Trans 48(25):9187–9193

    CAS  Article  Google Scholar 

  12. 12.

    Morgan IS, Mansikkamäki A, Zissimou GA, Koutentis PA, Rouziѐres M, Clérac R, Tuononen HM (2015) Coordination complexes of neutral 1,2,4-benzotriazinyl radical ligand: synthesis, molecular and electronic structures, and magnetic properties. Chem Eur J 21:15843–15753

    CAS  Article  Google Scholar 

  13. 13.

    Mondal D, Majee MC, Kundu S, Mörtel M, Abbas G, Endo A, Khusniyarov MM, Chaudhury M (2018) Dinuclear iron(III) and cobalt(III) complexes featuring a biradical bridge: their molecular structures and magnetic, spectroscopic, and redox properties. Inorg Chem 57:1004–1016

    CAS  Article  Google Scholar 

  14. 14.

    Nishijo J, Shima Y, Enomoto M (2017) Synthesis, crystal structures and magnetic properties of new chromium(III)-acetylide-TTF type complexes. Polyhedron 136:35–41

    CAS  Article  Google Scholar 

  15. 15.

    Nishijo J, Enomoto M (2013) A series of weak ferromagnets based on a chromium–Acetylide–TTF type complex: correlation of the structures and magnetic properties and origin of the weak ferromagnetism. Inorg Chem 52:13263–13268

    CAS  Article  Google Scholar 

  16. 16.

    Nishijo J (2013) Chromium-ethynyltetrathiafulvalene complex based magnetic materials. Polyhedron 66:43–47

    CAS  Article  Google Scholar 

  17. 17.

    Nishijo J, Judai K, Nishi N (2011) Weak ferromagnetism and strong spin−spin interaction mediated by the mixed-valence ethynyltetrathiafulvalene-type ligand. Inorg Chem 50:3464–3470

    CAS  Article  Google Scholar 

  18. 18.

    Kini AM, Parakka JP, Geiser U, Wang H, Rivas F, DiNino E, Thomas S, Dudek JD, Williamns JM (1999) Tetraalkyl- and dialkyl-substituted BEDT-TTF derivatives and their cation-radical salts: synthesis, structure, and properties. J Mater Chem 9:883–892

    CAS  Article  Google Scholar 

  19. 19.

    Mora H, Fabre J, Giral L, Montginoul C (1992) Sumtheses et caracterisation des derives methyles du tetrathiafulvalene; nouvelle voie d’acces au tetrathiafulvalene. Bull Soc Chim Belg 101:137–146

    CAS  Article  Google Scholar 

  20. 20.

    Haley NF, Fichtner MW (1980) Facile synthesis of 1,3-dithiol-2-ones and 1,3-dithiol-2-thiones. J Org Chem 45:2959–2962

    CAS  Article  Google Scholar 

  21. 21.

    Dinsmore A, Garner CD, Joule JA (1998) 4-(2,2-dimethyldioxalan-4-yl)-5-(quinoxalin-2-yl)-1,3-dithiol-2-one, a proligand relating to the cofactor of the oxomolybdoenzymes. Tetrahedron 54:3291–3302

    CAS  Article  Google Scholar 

  22. 22.

    Burla MC, Caliandro R, Camalli M, Carrozzini B, Cascarano GL, Caro LD, Giacovazzo C, Polidori G, Spagna R (2005) SIR2004: an improved tool for crystal structure determination and refinement. J Appl Cryst 38:381–388

    CAS  Article  Google Scholar 

  23. 23.

    Sheldrick GM (2015) Crystal structure refinement with SHELXL. Acta Cryst C 71:3–8

    Article  Google Scholar 

  24. 24.

    Segura JL, Martín N (2001) New concepts in tetrathiafulvalene chemistry. Angew Chem Int Ed 40:1372–1409

    CAS  Article  Google Scholar 

  25. 25.

    Zapata-Rivera J, Maynay D, Calzado CJ (2017) Evaluation of the magnetic interaction in salts containing [Ni(dmit)2] radical anions. Chem Mater 29:4317–4329

    CAS  Article  Google Scholar 

  26. 26.

    Bonner JC, Fisher ME (1964) Linear magnetic chains with anisotropic coupling. Phys Rev 135:A640-658

    Article  Google Scholar 

  27. 27.

    Estes WE, Gavel DP, Hatfield WE, Hodgson DJ (1978) Magnetic and structural characterization of dibromo- and dichlorobis(thiazole)copper(II). Inorg Chem 17:1415–1421

    CAS  Article  Google Scholar 

  28. 28.

    Nakajima H, Katsuhara M, Ashizawa M, Kawamoto T, Mori T (2004) Ferromagnetic anomaly associated with the antiferromagnetic transition in (Donor)[Ni(mnt)2]-type charge-transfer salts. Inorg Chem 43:6075–6082

    CAS  Article  Google Scholar 

  29. 29.

    Lopes G, Gama V, Simão D, Santos IC, Lopes EB, Pereira CJ, Almeida M, Rabaça S (2019) Structural relations in (1:1) and (2:1) cyanobenzene-ethylenedithio-TTF radical salts; the role of C≡N...H interactions. CrystEngComm 21:7489–7497

    CAS  Article  Google Scholar 

  30. 30.

    Allan ML, Coomber AT, Marsden IR, Martens JHF, Friend RH (1993) NH4Ni(mnt)2H2O - A low dimensional organic ferromagnet. Synth Metals 56(2–3):3317–3322

    CAS  Article  Google Scholar 

  31. 31.

    Coomber AT, Beljonne D, Friend RH, Brédas JL, Charlton A, Robertson N, Underhill AE, Kurmoo M, Day P (1996) Intermolecular interactions in the molecular ferromagnetic NH4Ni(mnt)2·H2O. Nature 380:144–146

    CAS  Article  Google Scholar 

  32. 32.

    Pullen AE, Faulmann C, Pokhodnya KI, Cassoux P, Tokumoto M (1998) Structural and magnetic properties of M(mnt)2 salts (M = Ni, Pt, Cu) with a ferrocene-based cation, [FcCH2N(CH3)3]+. Interplay between M...M and M...S intermolecular interactions. Inorg Chem 37:6714–6720

    CAS  Article  Google Scholar 

  33. 33.

    Weiher JF, Melby LR, Benson RE (1964) 1,2-dicyanoethylene-1,2-dithiolate chelates. J Am Chem Soc 86:4329–4333

    CAS  Article  Google Scholar 

  34. 34.

    Willett RD, Gómez-García CJ, Ramakrishna BL, Twamley B (2005) (NBu4)Ni(mnt)2: A novel bistable high temperature spin-Peierls-like system. Polyhedron 24:2232–2237

    CAS  Article  Google Scholar 

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Correspondence to Junichi Nishijo.

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Nishijo, J., Uchida, M., Enomoto, M. et al. A chromium(III) bis-acetylide complex containing a trans-diethyl-ethylenedithio-substituted tetrathiafulvalene (TTF) derivative: synthesis, crystal structures, and magnetic properties. Transit Met Chem (2021). https://doi.org/10.1007/s11243-021-00453-9

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