Journal of Chemical Sciences

, Volume 123, Issue 6, pp 807–818 | Cite as

Two new 1D chains of Ni 2 Na 2 heterometallic double half-cubane building units: Synthesis, structures and variable temperature magnetic study

  • KARTIK CHANDRA MONDAL
  • BAPPADITYA GOLE
  • YOU SONG
  • STUART R BATTEN
  • DAVID R TURNER
  • PARTHA SARATHI MUKHERJEE
Article

Abstract

An equimolar mixture of Ni(NO3)2·6H2O and pyridine-2-aldehyde with two equivalents of NaN3 in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide (DMF) yielded light green single crystals [{Ni2Na2(pic)4(N3)2(H2O)2(MeOH)}· MeOH·3H2O]n (1) and [{Ni2Na2(pic)4(N3)2(H2O)4}·2DMF·H2O]n (2) (pic = pyridine-2-carboxylate) at room temperature and high temperature (100°C), respectively. Variable temperature magnetic studies revealed the existence of overall ferromagnetic behaviour with J ≈ +10 cm − 1 and D ≈ − 2 to −7 cm − 1 for 1 and 2, respectively. Negative D values as well as variation of D upon slight distortion of structure by varying reaction temperature were observed. The X-band Electron Paramagnetic Resonance (EPR) spectra of both 2 and 3 were recorded below 50 K. The structural distortion was also implicated from the EPR spectra. Density Functional Theory (DFT) calculations on both complexes were performed in two different ways to corroborate the magnetic results. Considering only Ni\(^{\rm II}_{2}\) dimeric unit, results were J = +20.65 cm − 1 and D = −3.16 cm − 1 for 1, and J = +24.56 cm − 1 and D = −4.67 cm − 1 for 2. However, considering Ni\(^{\rm II}_{2}\)Na\(^{\rm I}_{2}\) cubane as magnetic core the results were J = +16.35 cm − 1 (1), +19.54 cm − 1 (2); D = −3.05 cm − 1 (1), −4.25 cm − 1 (2).

Graphical Abstract

Two new 1D chains of Ni2Na2heterometallic double half-cubane building units have been isolated from the reaction of a 1:1 mixture of Ni(NO3)2·6H2O and pyridine-2-aldehyde with two equivalents of NaN3 in the presence of NaOMe and their structures established by X-ray crystallography. The magnetic behaviour of the two complexes has been studied and DFT calculations performed to investigate the exchange mechanism.

Keywords

Coordination polymers cluster; Ni\(^{\rm II}_{2}\), 1D chain magnetism DFT 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Supplementary material

12039_2011_170_MOESM1_ESM.pdf (629 kb)
(PDF 628 KB)

References

  1. 1.
    Sessoli R, Tsai H-L, Schake A R, Wang S, Vincent J B, Folting K, Gatteschi D, Christou G and Hendrickson D N 1993 J. Am. Chem. Soc. 115 1804CrossRefGoogle Scholar
  2. 2.
    Sessoli R, Gatteschi D, Caneschi A and Novak M A 1993 Nature 365 141CrossRefGoogle Scholar
  3. 3.
    Mereacre V M, Ako A M, Clérac R, Wernsdorfer W, Filoti G, Bartolomé J, Anson C E and Powel A K 2007 J. Am. Chem. Soc. 129 9248CrossRefGoogle Scholar
  4. 4.
    Benelli C, Cano J, Journaux Y, Sessoli R, Solan G A and Winpenny R E P 2001 Inorg. Chem. 40 188CrossRefGoogle Scholar
  5. 5.
    Ako A M, Hewitt I J, Mereacre V, Clérac R, Wernsdorfer W, Anson C E and Powell A K 2006 Angew. Chem., Int. Ed. 45 4926CrossRefGoogle Scholar
  6. 6.
    Caneschi A, Gatteschi D, Sessoli R, Barra A L, Bruel L C and Guillot M 1991 J. Am. Chem. Soc. 113 5873CrossRefGoogle Scholar
  7. 7.
    Novitchi G, Wernsdorfer W, Chibotaru L F, Costes J-P, Anson C E and Powell A K 2009 Angew. Chem., Int. Ed. 48 1614CrossRefGoogle Scholar
  8. 8.
    Mishra A, Wernsdorfer W, Parson S, Christou G and Brechin E K 2005 Chem. Commun. 2086Google Scholar
  9. 9.
    Maspoch D, Ruiz-Molinaa D and Veciana J 2007 Chem. Soc. Rev. 36 770CrossRefGoogle Scholar
  10. 10.
    Gatteschi D and Sessoli R 2003 Angew. Chem., Int. Ed. 42 268CrossRefGoogle Scholar
  11. 11.
    Beauvais L G and Long J R 2002 J. Am. Chem. Soc. 124 12096CrossRefGoogle Scholar
  12. 12.
    Freedman D E, Harman W H, Harris T D, Long G J, Chang C J and Long J R 2010 J. Am. Chem. Soc. 132 1224CrossRefGoogle Scholar
  13. 13.
    Kahn O 1993 Molecular magnetism (VCH Weinheim: Germany)Google Scholar
  14. 14.
    Benelli C and Gatteschi D 2002 Chem. Rev. 102 2369CrossRefGoogle Scholar
  15. 15.
    Ginsberg A P, Brookes R W, Martin R L and Sherwood R C 1972 Inorg. Chem. 11 2884CrossRefGoogle Scholar
  16. 16.
    Journaux Y, Kahn O, Chevalier B, Etourneau J, Claude R and Dworkin A 1978 Chem. Phys. Lett. 55 140CrossRefGoogle Scholar
  17. 17.
    Joung K O, O’Connor C J, Sinn E and Carlin R L 1979 Inorg. Chem. 18 804CrossRefGoogle Scholar
  18. 18.
    Herchel R, Boča R, Krzystek J, Ozarowski A, Durán M and Slageren J V 2007 J. Am. Chem. Soc. 129 10306CrossRefGoogle Scholar
  19. 19.
    Escuer A, Vicente R, Ribas J and Solans X 1995 Inorg. Chem. 34 1793CrossRefGoogle Scholar
  20. 20.
    Mukherjee P, Drew M G B, Gómez-Gercía J J and Ghosh A 2009 Inorg. Chem. 48 5848CrossRefGoogle Scholar
  21. 21.
    Halcrow M A, Huffman J C and Christou G 1995 Angew. Chem., Int. Ed. 34 889CrossRefGoogle Scholar
  22. 22.
    Escuer A, Front-Berdia M, Kumar S B, Solans X and Vicente R 1999 Polyhedron 18 909CrossRefGoogle Scholar
  23. 23.
    Clemente-Juan J M, Andres H, Borrás-Almenar J J, Coronado E, Gudel H U, Aebersold M, Kearly G, Buttner H and Zolliker M 1999 J. Am. Chem. Soc. 121 10021CrossRefGoogle Scholar
  24. 24.
    Yang E-C, Wernsdorfer W, Zakharov L N, Karaki Y, Yamaguchi A, Isidro R M, Lu G-D, Wilson S A, Rheingold A L, Ishimoto H and Hendrickson D N 2006 Inorg. Chem. 45 529CrossRefGoogle Scholar
  25. 25.
    Lawrence J, Yang E-C, Edwards R, Olmstead M M, Ramsey C, Dalal N S, Gantzel S, Hill P K and Hendrickson D N 2008 Inorg. Chem. 47 1965CrossRefGoogle Scholar
  26. 26.
    Venegas-Yazigi D, Canob J, Ruiz E and Alvarez S 2006 Physica B 384 123CrossRefGoogle Scholar
  27. 27.
    Habib M, Karamakar T K, Aromi G, Ribas-Arino J, Fun H-K, Chantrapromma S and Chandra S K 2008 Inorg. Chem. 47 4109CrossRefGoogle Scholar
  28. 28.
    Sarkar S, Datta A, Mondal A, Chopra D, Ribas J, Rajak J J, Sairam S M and Pati S K 2006 J. Phys. Chem. B 110 12CrossRefGoogle Scholar
  29. 29.
    Brechin E K, Clegg W, Murrie M, Parsons S, Teat S J and Winpenny R E P 1998 J. Am. Chem. Soc. 120 7365CrossRefGoogle Scholar
  30. 30.
    Mandal D, Bertolasi V, Ribas-Ariño J, Aromí G and Ray D 2008 Inorg. Chem. 47 3465CrossRefGoogle Scholar
  31. 31.
    Blake A J, Grant C M, Parsons S, Rawson J M and Winpenny R E P 1994 J. Chem. Soc., Chem. Commun. 2363Google Scholar
  32. 32.
    Brechin E K, Gould R O, Harris S G, Parsons S and Winpenny R E P 1996 J. Am. Chem. Soc. 118 11293CrossRefGoogle Scholar
  33. 33.
    Park I-S and Hausinger R P 1995 Science 267 1156CrossRefGoogle Scholar
  34. 34.
    Papaefstathiou G S, Perlepes S P, Escuer A, Vicente R, Font-Bardia M and Solans X 2001 Angew. Chem., Int. Ed. 40 884CrossRefGoogle Scholar
  35. 35.
    Mondal K C, Sengupta O, Nethaji M and Mukherjee P S 2008 Dalton Trans. 767Google Scholar
  36. 36.
    Mondal K C and Mukherjee P S 2008 Inorg. Chem. 47 4215CrossRefGoogle Scholar
  37. 37.
    Mukherjee S, Gole B, Chakrabarty R and Mukherjee P S 2009 Inorg. Chem. 48 11325CrossRefGoogle Scholar
  38. 38.
    Mondal K C, Sengupta O and Mukherjee P S 2009 Inorg. Chem. Commun. 12 682CrossRefGoogle Scholar
  39. 39.
    Goher M A S and Mautner M A 1995 Polyhedron 14 1439CrossRefGoogle Scholar
  40. 40.
    SMART/SAINT, Bruker AXS 2004 Inc.: Madison WIGoogle Scholar
  41. 41.
    Sheldrick G M, SHELX-97 1998 Program for the Solution and Refinement of Crystal Structures (University of Göttingen, Göttingen, Germany)Google Scholar
  42. 42.
    Barbour L J 2001 J. Supramol. Chem. 1 189CrossRefGoogle Scholar
  43. 43.
    Farrugia L J 2003 WinGX: An Integrated System of Windows Programs for the Solution, Refinement and Analysis for Single Crystal X-ray Diffraction Data, version 1.65.04; Department of Chemistry: University of Glasgow (Farrugia L J 1999 J. Appl. Crystallogr. 32 837)Google Scholar
  44. 44.
    Sheldrick G M 1999 SADABS Bruker Nonius Area Detector Scaling and Absorption Correction, version 2.05; University of Göttingen, Göttingen, GermanyGoogle Scholar
  45. 45.
    Ruiz E, Alemany P, Alvarez S and Cano J 1997 J. Am. Chem. Soc. 119 1297CrossRefGoogle Scholar
  46. 46.
    Ruiz E, Rodríguez-Fortea A, Cano J, Alvarez S and Alemany P 2003 J. Comput. Chem. 24 982CrossRefGoogle Scholar
  47. 47.
    Ruiz E, Cano J, Alvarez S and Alemany P 1998 J. Am. Chem. Soc. 120 11122CrossRefGoogle Scholar
  48. 48.
    Becke A D 1993 J. Chem. Phys. 98 5648CrossRefGoogle Scholar
  49. 49.
    Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Montgomery J A, Vreven T, Kudin K N, Burant J C, Millam J M, Iyengar S S, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson G A, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida H, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox J E, Hratchian H P, Cross J B, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J, Ayala P Y, Morokuma K, Voth G A, Salvador P, Dannenberg J J, Zakrzewski V G, Dapprich S, Daniels A D, Strain M C, Farkas O, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Ortiz J V, Cui Q, Baboul A G, Clifford S, Cioslowski J, Stefanov B B, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin R L, Fox D J, Keith T, Al-Laham M A, Peng C Y, Nanayakkara A, Challacombe M, Gill P M W, Johnson B, Chen W, Wong M W, Gonzalez C and Pople J A 2003 Gaussian 03, revision B.4; Gaussian Inc.: Pittsburgh, PAGoogle Scholar
  50. 50.
    Becke A D 1988 Phys. Rev. A 38 3098CrossRefGoogle Scholar
  51. 51.
    Lee C, Yang W and Parr R G 1988 Phys. Rev. B 37 785CrossRefGoogle Scholar
  52. 52.
    Ruiz E, Alvarez S, Cano J and Polo V 2005 J. Chem. Phys. 123 164110CrossRefGoogle Scholar
  53. 53.
    Ribas J, Escuer A, Monfort M, Vicente R, Cortes R, Lezama L and Roji T 1999 Coord. Chem. Rev. 193–195 1027CrossRefGoogle Scholar
  54. 54.
    Cortés R, Lezama L and Rojo T 1994 IEEE Trans. Magn. 30 4728CrossRefGoogle Scholar
  55. 55.
    Deveson A C, Heath S L, Harding C J and Powell A K 1996 J. Chem. Soc., Dalton Trans. 3173Google Scholar
  56. 56.
    Papadopoulos A, Tangoulis V, Raptopoulou C P, Terzis A, Kessissoglou D P 1996 Inorg. Chem. 35 559CrossRefGoogle Scholar
  57. 57.
    Bradford P, Hynes R C, Payne N C and Willis C J 1990 J. Am. Chem. Soc. 112 2647CrossRefGoogle Scholar
  58. 58.
    Tangoulis V, Paschalidou S, Bakalbassis E G, Perlepes S P, Raptopoulou C P and Terzis A T A 1997 Angew. Chem., Int. Ed. 36 1083CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2011

Authors and Affiliations

  • KARTIK CHANDRA MONDAL
    • 1
  • BAPPADITYA GOLE
    • 1
  • YOU SONG
    • 2
  • STUART R BATTEN
    • 3
  • DAVID R TURNER
    • 3
  • PARTHA SARATHI MUKHERJEE
    • 1
  1. 1.Department of Inorganic and Physical ChemistryIndian Institute of ScienceBangaloreIndia
  2. 2.State Key Laboratory of Coordination ChemistryNanjing UniversityNanjingChina
  3. 3.School of ChemistryMonash UniversityMonashAustralia

Personalised recommendations