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Iron(III) and cyano-bridged dinuclear copper(II) complexes: synthesis, structures and magnetic property of the copper(II) complex

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Abstract

This report describes the synthesis and structural characterizations of three new complexes; [Na3Fe2(bbp)(Hbbp)(CN)6(H2O)9]·4H2O (1), (Bu4N)[Fe(bbp)2]·3CH3OH·2H2O (2), and a cyano-bridged dinuclear copper(II) complex, [Cu2(tren)2(CN)][Fe(bbp)2]3· 6CH3OH·4H2O (3), where H2bbp = bis(2-benzimidazolyl)pyridine and tren = tris(2-aminoethyl)amine. X-ray crystallography reveals that the geometry of iron(III) centers in the complex anions of 1–3 is an octahedral, while it is a trigonal bipyramidal around copper(II) center in the complex cation of 3. Both bbp ligands meridionally coordinate iron(III) centers in the complex cations of 2 and 3, while three cyanide ions and bbp (or Hbbp) ligand occupied either of the meridional positions around the metal center in 1. In the dinuclear complex cation of 3, the Cu(II)-CN-Cu(II) bridging region is strictly linear as dictated by the symmetry with Cu···Cu separation of 5.084 (7) Å. Variable temperature magnetic susceptibility study shows that the cyano-bridge mediates the antiferromagnetic coupling between copper(II) centers with J value of −110 K in 3.

Graphic abstract

Two Fe(III) complexes and one heterobimetallic Fe(III)–Cu(II) complex have been synthesized and X-ray crystallographically characterized. Variable temperature magnetic susceptibility study revealed the antiferromagnetic coupling between the Cu(II) centers in Fe(III)–Cu(II) complex. The magneto-structural correlation has been further established.

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References

  1. Shatruk M, Avendano C and Dunbar K R 2009 Cyanide-bridged complexes of transition metals: a molecular magnetism perspective Prog. Inorg. Chem. 56 155

    Article  CAS  Google Scholar 

  2. Richardson G N, Brand U and Vahrenkamp H 1999 Linear and bent M(μ-CN)Pt(μ-CN)M chains:  probes for remote metal–metal interactions Inorg. Chem. 38 3070

    Article  CAS  Google Scholar 

  3. Kaye S S and Long J R 2007 The role of vacancies in the hydrogen storage properties of Prussian blue analogues Catal. Today 120 311

    Article  CAS  Google Scholar 

  4. (a) Herrera J M, Marvaud V, Verdaguer M, Marrot J, Kalisz M and Mathonière C 2004 reversible photoinduced magnetic properties in the heptanuclear complex [MoIV(CN)2(CN-CuL)6]8+: a photomagnetic high-spin molecule Angew. Chem. Int. Ed. 43 5468; (b) Long J, Chamoreau L M, Mathonière C and Marvaud V 2009 Photoswitchable heterotrimetallic chain based on octacyanomolybdate, copper, and nickel: synthesis, characterization, and photomagnetic properties Inorg. Chem. 48 22; (c) Freedman D E, Jenkins D M, Iavarone A T and Long J R 2008 A redox-switchable single-molecule magnet incorporating [Re(CN)7]3– J. Am. Chem. Soc. 130 2884; (d) Sutter J P, Dhers S, Rajamani R, Ramasesha S, Costes J P, Duhayon C and Vendier L 2009 Hetero-metallic {3d-4f-5d} complexes: preparation and magnetic behavior of trinuclear [(LMe2Ni–Ln){W(CN)8}] compounds (Ln = Gd, Tb, Dy, Ho, Er, Y; LMe2 = Schiff base) and variable SMM characteristics for the Tb derivative Inorg. Chem. 48 5820; (e) Goodwin A L, Kennedy B J and Kepert C 2009 Thermal expansion matching via framework flexibility in zinc dicyanometallates J. Am. Chem. Soc. 131 6334; (f) Choi H J, Sokol J J and Long J R, 2004 Raising the spin-reversal barrier in cyano-bridged single-molecule magnets: linear Mn III2 MIII(CN)6 (M = Cr, Fe) species incorporating [(5-Brsalen)Mn]+ units Inorg. Chem. 43 1606; (g) Ferbinteanu M, Miyasaka H, Wernsdorfer W, Nakata K, Sugiura K, Yamashita M, Coulon C and Clérac R 2005 Single-chain magnet (NEt4)[Mn2(5-MeOsalen)2Fe(CN)6] made of MnIII–FeIII–MnIII trinuclear single-molecule magnet with an ST = 9/2 spin ground state J. Am. Chem. Soc. 127 3090; (h) Toma L M, Lescouëzec R, Pasan J, Ruiz-Perez C, Vaissermann J, Cano J, Carrasco R, Wernsdorfer W, Lloret F and Julve M, 2006 [Fe(bpym)(CN)4]−: a new building block for designing single-chain magnets J. Am. Chem. Soc. 128 4842; (i) Choi S W, Kwak H Y, Yoon J H, Kim H C, Koh E K and Hong C S 2008 Intermolecular contact-tuned magnetic nature in one-dimensional 3d-5d bimetallic systems: from a metamagnet to a single-chain magnet Inorg. Chem. 47 10214; (j) Miyasaka H, Julve M, Yamashita M and Clérac R 2009 Slow dynamics of the magnetization in one-dimensional coordination polymers: single-chain magnets Inorg. Chem. 48 3420; (k) Harris T D, Bennett M V, Clérac R and Long J R 2010 [ReCl4(CN)2]2−: A high magnetic anisotropy building unit giving rise to the single-chain magnets (DMF)4MReCl4(CN)2 (M = Mn, Fe, Co, Ni) J. Am. Chem. Soc. 132 3980; (l) Zhang Y J, Liu T, Kanegawa S and Sato O 2009 Reversible single-crystal-to-single-crystal transformation from achiral antiferromagnetic hexanuclears to a chiral ferrimagnetic double zigzag chain J. Am. Chem. Soc. 131 7942; (m) Funck K E, Hilfiger M G, Berlinguette C P, Shatruk M, Wernsdorfer W and Dunbar K R 2009 Trigonal-bipyramidal metal cyanide complexes: a versatile platform for the systematic assessment of the magnetic properties of Prussian blue materials Inorg. Chem. 48 3438; (n) Maxim C, Sorace L, Khuntia P, Madalan A M, Kravtsov V, Lascialfari A, Caneschi A, Journaux Y and Andruh M 2010 A missing high-spin molecule in the family of cyanido-bridged heptanuclear heterometal complexes, [(LCu(II))6Fe(III)(CN)6]3+, and its Co(III) and Cr(III) analogues, accompanied in the crystal by a novel octameric water cluster Dalton Trans. 39 4838

  5. (a) Ferlay S, Mallah T, Ouahes R, Veillet P and Verdaguer M 1995 A room-temperature organometallic magnet based on Prussian blue Nature 378 701; (b) Holmes S M and Girolami G S 1999 Sol-gel synthesis of KVII[CrIII(CN)6].2H2O: A crystalline molecule-based magnet with a magnetic ordering temperature above 100 °C J. Am. Chem. Soc. 121 5593; (c) Hatlevik Ø, Buschmann W E, Zhang J, Manson J L and Miller J S 1999 Enhancement of the magnetic ordering temperature and air stability of a mixed valent vanadium hexacyanochromate(III) magnet to 99 °C (372 K) Adv. Mater. 11 914; (d) Sato O, Iyoda T, Fujishima A and Hashimoto K 1996 Photoinduced magnetization of a cobalt-iron cyanide Science 272 704; (e) Chorazy S, Stanek J J, Nogaś W, Majcher A M, Rams M, Kozieł M, Juszyńska-Gałązka E, Nakabayashi K, Ohkoshi S I, Sieklucka B and Podgajny R 2016 Tuning of charge transfer assisted phase transition and slow magnetic relaxation functionalities in {Fe9–xCox[W(CN)8]6} (x = 0–9) Molecular Solid Solution J. Am. Chem. Soc. 138 1635

    Google Scholar 

  6. Rodriguez-Fortea A, Alemany P, Alvarez S, Ruiz E, Scuiller A, Decroix C, Marvaud V, Vaissermann J, Verdaguer M, Rosenman I and Julve M. 2001 Exchange coupling in cyano-bridged homodinuclear cu(ii) and ni(ii) complexes: synthesis, structure, magnetism, and density functional theoretical study Inorg. Chem. 40 5868

    CAS  Google Scholar 

  7. (a) Jeon I R, Calancea S, Panja A, Piñero Cruz D M, Koumousi E S, Dechambenoit P, Coulon C, Wattiaux A, Rosa P, Mathonière C and Clérac R 2013 Spin crossover or intra-molecular electron transfer in a cyanido-bridged fe/co dinuclear dumbbell: a matter of state Chem. Sci. 4 2463; (b) Jafri S F, Koumousi E S, Arrio M A, Juhin A, Mitcov D, Rouzières M, Dechambenoit P, Li D, Otero E, Wilhelm F, Rogalev A, Joly L, Kappler J P, dit Moulin C C, Mathonière C, Clérac R and Sainctavit P 2019 Atomic scale evidence of the switching mechanism in a photomagnetic CoFe dinuclear Prussian Blue Analogue J. Am. Chem. Soc. 141 3470

  8. Reger D L, Pascui A E, Smith M D, Jezierska J and Ozarowski A 2015 Synthesis, structural, magnetic and electron paramagnetic resonance studies of monobridged cyanide and azide dinuclear copper(II) complexes: antiferromagnetic superexchange interactions Inorg. Chem. 54 1487

    Article  CAS  Google Scholar 

  9. Parker R J, Spiccia L, Moubaraki B, Murray K S, Skelton B W and White A H 2000 Cyano bridged dinuclear Cu(II) complexes Inorg. Chim. Acta. 300–302 922

    Article  Google Scholar 

  10. (a) Addison A W and Burke P J 1981 Synthesis of some imidazole‐ and pyrazole‐ derived chelating agents J. Heterocyclic Chem. 18 803; (b) Panja A, Goswami S, Shaikh N, Roy P, Manassero M, Butcher R J and Banerjee P 2005 Synthesis and X-ray crystallographic characterization of copper and iron complexes with tetradentate-N4 ligands: reactivity towards catechol oxidation Polyhedron 24 2912

  11. Otwinowski Z and Minor W 1997 Processing of X-ray diffraction data collected in oscillation mode Methods Enzymol. 276 307

    Article  CAS  Google Scholar 

  12. Sheldrick G M 2015 SHELXT—Integrated space-group and crystal-structure determination Acta Cryst. A71 3

  13. Panja A, Guionneau P, Jeon I R, Holmes S M, Clérac R and Mathonière C 2012 Syntheses, structures, and magnetic properties of a novel mer-[(bbp)FeIII(CN)3]2− building block (bbp: bis(2-benzimidazolyl)pyridine dianion) and its related heterobimetallic Fe(III)−Ni(II) complexes Inorg. Chem. 51 12350

    Article  CAS  Google Scholar 

  14. Lescouëzec R, Vaissermann J, Toma L M, Carrasco R, Lloret F and Julve M 2004 mer-[FeIII(bpca)(CN)3]−: A new low-spin iron(III) complex to build heterometallic ladder-like chains Inorg. Chem. 43 2234

    Article  Google Scholar 

  15. Ni Z H, Kou H Z, Zhang L F, Ni W W, Jiang Y B, Cui A L, Ribas J and Sato O 2005 mer-[Fe(pcq)(CN)3]−:  A novel cyanide-containing building block and its application to assembling cyanide-bridged trinuclear Fe III2 MnII complexes [pcq− = 8-(Pyridine-2-carboxamido)quinoline Anion] Inorg. Chem. 44 9631

    Article  CAS  Google Scholar 

  16. Kim J I, You H S, Koh E K, Kim H C and Hong C S 2007 Ferrimagnetic FeIII-MnIII zigzag chain formed by a new mer-positioned iron(III) cyanide precursor Inorg. Chem. 46 8481

    Article  CAS  Google Scholar 

  17. Kim J I, You H S, Koh E K and Hong C S 2007 Field-induced metamagnetic transition in the FeIII–MnIII bimetallic chain built by a new cyanide-bearing FeIII precursor Inorg. Chem. 46 10461

    Article  CAS  Google Scholar 

  18. Kim J I, Kwak H Y, Yoon J H, Ryu D W, You I Y, Yang N, Cho B K, Park J G, Lee H and Hong C S 2009 Cyanide-bridged FeIII–MnIII bimetallic complexes with dimeric and chain structures constructed from a newly made mer-Fe tricyanide: structures and magnetic properties Inorg. Chem. 48 2956

    Article  CAS  Google Scholar 

  19. Addision A W, Rao T N, Reedijik J, Rijn J V and Verschoor G C 1984 Synthesis, structure, and spectroscopic properties of copper(II) compounds containing nitrogen-sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper(II) perchlorate J. Chem. Soc. Dalton. Trans. 1349

  20. Jungst R and G Stucky 1974 Monobridged inner-sphere dimer. X-ray crystal structure of µ-cyano bis(5,7,7,12,14,14-hexamethyl-1-1,4,8,11-tetraazacyclotetradeca-4,11-diene) dicopper(II) perchlorate Inorg. Chem. 13 2404

  21. Bieksza D S and Hendrickson D N 1977 Magnetic exchange in transition metal dimers. 9. Copper(II) dimers with single end-to-end cyanide bridges and unusual electron paramagnetic resonance spectra Inorg. Chem. 16 924

  22. Scott M J, Lee S C and Holm R H 1944 Synthesis and structural characterization of unsupported [FeIII–CN–CuII] bridges related to that in cyanide-inactivated cytochrome c oxidase Inorg. Chem. 33 4651

    Article  Google Scholar 

  23. Bulach V, Duval H, Fischer J and Weiss R 1977µ-Cyano-bis(2,2′:6′,2′′terpyridineN,N′,N′′dicopper(II) Perchlorate Acetonitrile, [Cu2(CN)(Cl5H11N3)2](ClO4)3.CH3CN Acta Crystallogr. C 53 543

  24. Karlin K D, Hayes J C, Juen S, Hutchinson J P and Zubieta J 1982 Tetragonal vs. trigonal coordination in copper(II) complexes with tripod ligands: structures and properties of [Cu(C21H24N4)Cl]PF6 and [Cu(C18H18N4)Cl]PF6 Inorg. Chem. 21 4106

  25. Jacobson R R, Tyeklár Z, Karlin K D and Zubieta J 1991 Investigations of the technetium-hydrazido core. Synthesis and structural characterization of [(n-C4H9)4N][Tc2(NNPh2)2(C6Cl4O2)4].CH2Cl2.2CH3OH, a Tc(V)/Tc(VI) catecholate complex with the hydrazido ligands adopting the unusual η1 bridging mode Inorg Chem. 30 2035

  26. Komeda N, Nagao H, Kushi Y, Adachi G, Suzuki M, Uehara A and Tanaka K 1995 Molecular structure of nitro- and nitrito-copper complexes as reaction intermediates in electrochemical reduction of nitrite to dinitrogen oxide Bull. Chem. Soc. Jpn. 68 581

    Article  CAS  Google Scholar 

  27. Nanthakumar A, Fox S, Murthy N N, Karlin K D, Ravi N, Huynh B H, Orosz R D, Day E P and Hagen K S 1993 Oxo- and hydroxo-bridged (porphyrin)iron(III)–copper(II) species as cytochrome c oxidase models: acid-base interconversions and x-ray structure of the Fe(III)–(O2−)–Cu(II) complex J. Am. Chem. Soc. 115 8513

    Article  CAS  Google Scholar 

  28. Komeda N, Nagao H, Adachi G, Suzuki M, Uehara A and Tanaka K 1993 Molecular structure of copper nitrito complex as the reaction intermediate of dissimilatory reduction of NO2− Chem. Lett. 22 1521

    Article  Google Scholar 

  29. Atanasov M, Comba P, Hanson G R, Hausberg S, Helmle S and Wadepohl H 2011 Cyano-bridged homodinuclear copper(II) complexes Inorg. Chem. 50 6890

    Article  CAS  Google Scholar 

  30. Duggan D M, Jungst R G, Mann K R, Stucky G D and Hendrickson D N 1974 Electronic and crystallographic study of two cyanide-bridged copper(II) dimers. Magnetic exchange interactions through a linear copper-cyanide-copper bridge and a hydrogen-bonded copper-cyanide…hydrogen-nitrogen-copper system J. Am. Chem. Soc. 96 3443

  31. Lu T, Zhuang X, Li Y and Chen S 2004 C−C Bond cleavage of acetonitrile by a dinuclear copper(II) Cryptate J. Am. Chem. Soc. 126 4760

    Article  CAS  Google Scholar 

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Acknowledgements

AP gratefully acknowledges the financial support of this work by the CSIR, New Delhi, India (sanction no. 01(2834)/15/EMR-II dated 02/06/15). We would also like to thank Prof. Corine Mathonière, Université de Bordeaux, ICMCB, UPR 9048, Pessac F-33600, France and Prof. Rodolphe Clérac, Université Bordeaux, CRPP, UPR 8641, Pessac, F-33600, France for magnetic studies.

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  1. Department of Chemistry, Gokhale Memorial Girls’ College, 1/1 Harish Mukherjee Road, Kolkata, 700 020, India

    Goutam Mahata & Anangamohan Panja

  2. Department of Chemistry, Panskura Banamali College, Panskura, 721 152, India

    Anangamohan Panja

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  1. Goutam Mahata
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Mahata, G., Panja, A. Iron(III) and cyano-bridged dinuclear copper(II) complexes: synthesis, structures and magnetic property of the copper(II) complex. J Chem Sci 132, 102 (2020). https://doi.org/10.1007/s12039-020-01807-z

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