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Magnetic Properties, EPR, and Paramagnetic NMR Spectra of Cage Metal Complexes

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Abstract

Magnetometry, EPR, and NMR methods have been widely used to study electronic structure of paramagnetic transition d- and f-metal cage complexes, their magnetic characteristics, and SCO and SMM behavior of the (pseudo)clathrochelates as well as to deduce the geometry of coordination polyhedra of encapsulated metal ion(s).

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References

  1. Symons MCR, Taiwo T, Sargeson AM, Ali MM, Tabl AS (1996) EPR spectra for high- and low-spin CoII encapsulated complexes. Inorg Chim Acta 241:5–8

    Article  CAS  Google Scholar 

  2. Perraud O, Tommasino J-B, Robert V, Albela B, Khrouz L, Bonneviot L, Dutasta J-P, Martinez A (2013) Hemicryptophane-assisted electron transfer: a structural and electronic study. Dalton Trans 42:1530–1535

    Article  CAS  Google Scholar 

  3. Voloshin YZ, Varzatskii OA, Vorontsov II, Antipin MY (2005) Tuning a metal’s oxidation state: the potential of clathrochelate systems. Angew Chem Int Ed 44:3400–3402

    Article  CAS  Google Scholar 

  4. Azarkh M, Penkova LV, Kats SV, Varzatskii OA, Voloshin YZ, Groenen EJJ (2014) A mononuclear Mn(II) pseudoclathrochelate complex studied by multi-frequency electron-paramagnetic-resonance spectroscopy. J Phys Chem Lett 5:886–889

    Article  CAS  Google Scholar 

  5. Belov AS, Belaya IG, Novikov VV, Starikova ZA, Polshin EV, Dolganov AV, Lebed EG (2013) Structure, spectral and electrochemical properties of the 2,6-di-tert-butylphenol-functionalized iron and cobalt(II) clathrochelates and their phenylsulfide analogs. Inorg Chim Acta 394:269–281

    Article  CAS  Google Scholar 

  6. Varzatskii OA, Penkova LV, Kats (Menkach) SV, Dolganov AV, Vologzhanina AV, Pavlov AA, Novikov VV, Bogomyakov AS, Nemykin VN, Voloshin YZ (2014) Chloride ion-aided self-assembly of the pseudo-clathrochelate metal tris-pyrazoloximates. Inorg Chem 53:3062–3071

    Google Scholar 

  7. Voloshin YZ, Varzatskii OA, Novikov VV, Strizhakova NG, Vorontsov II, Vologzhanina AV, Lyssenko KA, Romanenko GV, Fedin MV, Ovcharenko VI, Bubnov YN (2010) Tris-dioximate cobalt(I, II, and III) clathrochelates: stabilization of different oxidation and spin states of an encapsulated metal ion by ribbed functionalization. Eur J Inorg Chem 2010:5401–5415

    Article  Google Scholar 

  8. Burdukov AB, Boguslavsky EG, Reznikov VA, Pervukhina NV, Vershinin MA, Voloshin YZ, Varzatskii OA, Bubnov YN (2005) Cage complexes as a molecular scaffold for assembling of polyfunctional and multicentered systems: synthesis and structures of the first nitroxide clathrochelates. Russ Chem Bull Int Ed 54:1125–1130

    Article  CAS  Google Scholar 

  9. Voloshin YZ, Varzatskii OA, Belov AS, Starikova ZA, Dolganov AV, Novikov VV, Bubnov YN (2011) Synthesis, structural and electrochemical features of alicyclic and aromatic α,α′-N2- and -S2-dioximate macrobicyclic cobalt(II,III) and ruthenium(II) tris-complexes. Inorg Chim Acta 370:322–332

    Google Scholar 

  10. Belaya IG, Belov AS, Platonov VE, Maksimov AM, Vologzhanina AV, Starikova ZA, Dolganov AV, Novikov VV, Bubnov YN (2012) Formation of the second superhydrophobic shell around an encapsulated metal ion: synthesis, X-ray structure and electrochemical study of the clathrochelate and bis-clathrochelate iron(II) and cobalt(II, III) dioximates with ribbed perfluoroarylsulfide substituents. Dalton Trans 41:737–746

    Article  Google Scholar 

  11. Voloshin YZ, Lebedev AY, Novikov VV, Dolganov AV, Vologzhanina AV, Lebed EG, Pavlov AA, Starikova ZA, Buzin MI, Bubnov YN (2013) Template synthesis, X-ray structure, spectral and redox properties of the paramagnetic alkylboron-capped cobalt(II) clathrochelates and their diamagnetic iron(II)-containing analogs. Inorg Chim Acta 399:67–78

    Article  CAS  Google Scholar 

  12. Novikov VV, Ananyev IV, Pavlov AA, Fedin MV, Lyssenko KA, Voloshin YZ (2014) Spin crossover anticooperativity induced by weak intermolecular interactions. J Phys Chem Lett 5:496–500

    Article  CAS  Google Scholar 

  13. Novikov VV, Pavlov AA, Belov AS, Vologzhanina AV, Savitsky A, Voloshin YZ (2014) Transition ion strikes back: large magnetic susceptibility anisotropy in cobalt(II) clathrochelates. J Phys Chem Lett 5:3799–3803

    Article  CAS  Google Scholar 

  14. Vologzhanina AV, Belov AS, Novikov VV, Dolganov AV, Romanenko GV, Ovcharenko VI, Korlyukov AA, Buzin MI, Voloshin YZ (2015) Synthesis and temperature-induced structural phase and spin transitions in hexadecylboron-capped cobalt(II) hexachloroclathrochelate and its diamagnetic iron(II)-encapsulating analogue. Inorg Chem 54:5827–5838

    Article  CAS  Google Scholar 

  15. Dolganov AV, Belov AS, Novikov VV, Vologzhanina AV, Romanenko GV, Budnikova YG, Zelinskii GE, Buzin MI, Voloshin YZ (2015) First iron and cobalt(II) hexabromoclathrochelates: structural, magnetic, redox and electrocatalytic behavior. Dalton Trans 44:2476–2487

    Article  CAS  Google Scholar 

  16. Novikov VV, Pavlov AA, Nelyubina YV, Boulon ME, Varzatskii OA, Voloshin YZ, Winpenny REP (2015) A trigonal prismatic mononuclear cobalt(II) complex showing single-molecule magnet behavior. J Am Chem Soc 137:9792–9795

    Article  CAS  Google Scholar 

  17. Pavlov AA, Nelyubina YV, Kats SV, Penkova LV, Efimov NN, Dmitrienko AO, Vologzhanina AV, Belov AS, Voloshin YZ, Novikov VV (2016) Polymorphism in a cobalt-based single-ion magnet tuning its barrier to magnetization relaxation. J Phys Chem Lett 7:4111–4116

    Article  CAS  Google Scholar 

  18. Vershinin MA, Burdukov AB, Eltsov IV, Reznikov VA, Boguslavsky EG, Voloshin YZ (2011) Unexpected radical substitution of the dichlorine-containing iron(II) clathrochelate with 1,4-dioxane derivatives: novel approach to functionalization of its macrobicyclic framework. Polyhedron 30:1233–1237

    Article  CAS  Google Scholar 

  19. Burdukov AB, Vershinin MA, Boguslavsky EG, Eltsov IV, Romanenko GV, Belov AS, Voloshin YZ (2013) New hydroxylamine-containing macrobicyclic encapsulating ligand: unexpected double addition of ethyl radicals to the azomethine fragment of a boron-capped iron(II) clathrochelate dioximate. Inorg Chem Commun 36:117–121

    Article  CAS  Google Scholar 

  20. Avecila F, Platas-Iglesias C, Rodríguez-Cortiñas R, Guillemot G, Bünzli JCG, Brondino CD, Geraldes CFGC, de Blas A, Rodríguez-Blas T (2002) Structural characterisation, EPR and magnetic properties of f–f and f–d lanthanide(III) phenolic cryptates. J Chem Soc Dalton Trans 4658–4665

    Google Scholar 

  21. Khanra S, Weyhermüller T, Bill E, Chaudhuri P (2006) Deliberate synthesis for magnetostructural study of linear tetranuclear complexes BIIIMnIIMnIIBIII, MnIIIMnIIMnIIMnIII, MnIVMnIIMnIIMnIV, FeIIIMnIIMnIIFeIII, and CrIIIMnIIMnIICrIII. Influence of terminal ions on the exchange coupling. Inorg Chem 45:5911–5923

    Article  CAS  Google Scholar 

  22. Platas C, Avecilla F, de Blas A, Geraldes CFGC, Rodríguez-Blas T, Adams H, Mahía J (1999) 1H NMR in solution and solid state structural study of lanthanide(III) cryptates. Inorg Chem 38:3190–3199

    Article  CAS  Google Scholar 

  23. Leniec G, Typek J, Kaczmarek SM (2008) Magnetic properties of a new Er(III) macrobicyclic complex studied by EPR. Appl Magn Res 35:197–203

    Article  CAS  Google Scholar 

  24. McInnes EJL, Timco GA, Whitehead GFS, Winpenny REP (2015) Heterometallic rings: their physics and use as supramolecular building blocks. Angew Chem Int Ed 54:14244–14269

    Article  CAS  Google Scholar 

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Voloshin, Y., Belaya, I., Krämer, R. (2017). Magnetic Properties, EPR, and Paramagnetic NMR Spectra of Cage Metal Complexes. In: Cage Metal Complexes. Springer, Cham. https://doi.org/10.1007/978-3-319-56420-3_4

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