Spin-State Switching in Solution

Spin-Crossover Materials: Properties and Applications

Volumn , Issue , 2013, Pages 281-301

  Shores, Matthew P ^a   Klug, Christina M ^a   Fiedler, Stephanie R ^a  

^a Department of Ecosystem Science and Sustainability   (United States)

Author keywords

Electronic absorption spectroscopy; Isomerization; Ligation changes; Metal centers; NMR characterization; Solution investigations; Spin crossover (SC); Spin state switching; SQUID Magnetometry

Indexed keywords

EID: 84886490571     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9781118519301.ch10     Document Type: Chapter

References (99)

1. Toftlund, H. (1989). Spin equilibria in iron(II) complexes. Coord. Chem. Rev., 94: 67-108.
2. Toftlund, H. (2001). Spin equilibrium in solutions. Monatsh. Chem., 132: 1269-1277.
3. Brady, C., McGarvey, J. J., McCusker, J. K., Toftlund, H., Hendrickson, D. N. (2004). Time-resolved relaxation studies of spin crossover systems in solution, in: Gütlich, P., Goodwin, H. A. (Eds) Spin Crossover in Transition Metal Compounds III. Top. Curr. Chem., 235: 1-22.
4. Toftlund, H., McGarvey, J. J. (2004). Iron(II) spin crossover systems with multidentate ligands, in: Gütlich, P., Goodwin, H. A. (Eds) Spin Crossover in Transition Metal Compounds I. Top. Curr. Chem., 233: 151-166.
5. Hassan, N., Koudriavtsev, A. B., Linert,W. (2008). Isoequilibrium relationships and cooperative effects in spin-state transitions in solution. Pure Appl. Chem., 80: 1281-1292.
6. Miller, J. S., Min, K. S. (2009). Oxidation leading to reduction: redox-induced electron transfer (RIET). Angew. Chem. Int. Ed., 48: 262-272.
7. Haynes, W. M. (Ed.) CRC Handbook of Chemistry and Physics, 92nd edn. CRC Press, Boca Raton, FL., USA.
8. Yaws, C. L. (2003) Yaws' handbook of thermodynamic and physical properties of chemical compounds. Knovel Corp., http://www.knovel.com.
9. Evans, D. F. (1959) The determination of the paramagnetic susceptibility of substances in solution by nuclear magnetic resonance. J. Chem. Soc., 2003-2005.
10. Crawford, T. H., Swanson, J. (1971) Temperature dependent magnetic measurements and structural equilibria in solution. J. Chem. Educ., 48: 382-386.
11. Live, D. H., Chan, S. I. (1970). Bulk susceptibility corrections in nuclear magnetic resonance experiments using superconducting solenoids. Anal. Chem., 42: 791-792.
12. Schubert, E. M. (1992) Utilizing the Evans method with a superconducting NMR spectrometer in the undergraduate laboratory. J. Chem. Educ., 69: 62.
13. Grant, D. H. (1995). Paramagnetic susceptibility by NMR: the "solvent correction" reexamined. J. Chem. Educ., 72: 39-40.
14. Ni, Z., McDaniel, A. M., Shores, M. P. (2010). Ambient temperature anion-dependent spin state switching observed in "mostly low spin" heteroleptic iron(II) diimine complexes. Chem. Sci., 1: 615-621.
15. Ostfeld, D., Cohen, I. A. (1972). A cautionary note on the use of the Evans method for magnetic moments. J. Chem. Educ., 49: 829.
16. Yatsunyk, L. A., Walker, F. A. (2004). Structural, NMR, and EPR studies of S = 1/2 and S = 3/2 Fe(III) bis(4-cyanopyridine) complexes of dodecasubstituted porphyrins. Inorg. Chem., 43: 757-777.
17. 2 coordination sphere-the influence of covalent linkers on cooperative interactions. Coord. Chem. Rev., 253: 2432-2449.
18. Weber, B., Walker, F. A. (2007). Solution NMR studies of iron(II) spin-crossover complexes. Inorg. Chem., 46: 6794-6803.
19. Berry, J. F., Cotton, F. A., Lu, T., Murillo, C. A. (2003). Increasing solubility and stability of linear tricobalt(II) chains with depa (diethyldipyridylamide) ligands. Inorg. Chem., 42: 4425-4430.
20. Ozarowski, A., Zvyagin, S. A., Reiff,W. M., Telser, J., Brunel, L.-C., Krzystek, J. (2004). High-frequency and-field epr of a pseudo-octahedral complex of high-spin Fe(II): bis(2,2⇌-bi-2-thiazoline)bis(isothiocyanato)iron(II). J. Am. Chem. Soc., 126: 6574-6575.
21. Gütlich, P., Hauser, A., Spiering, H. (1994). Thermal and optical switching of iron(II) complexes. Angew. Chem. Int. Ed., 33: 2024-2054.
22. Siretanu, D., Li, D., Buisson, L., Bassani, D. M., Holmes, S. M., Mathonière, C., Clérac, R. (2011). Controlling thermally induced electron transfer in cyano-bridged molecular squares: from solid state to solution. Chem. Eur. J., 17: 11704-11708.
23. 1) transitions in transitions in frozen solutions of iron(II) complexes-1 bis[2-(2-pyridylamino)-4-(2-pyridyl)thiazolato]iron(II). J. Inorg. Nucl. Chem., 39: 1131-1135.
24. III single-molecule magnets. Chem. Sci., 1: 631-636.
25. Tobinaga, H., Suehiro, M., Ito, T., Zhou, G., Karasawa, S., Koga, N. (2007). Magnetic property of 1: 2 mixture of Co(p-tolsal)2; p-tolsal = N-p-tolylsalicylideniminato, and cyclic pentacarbene-pyridine with S = 10/2 in dilute frozen solution. Polyhedron, 26: 1905-1911.
26. Ni, Z., Shores, M. P. (2009). Magnetic observation of anion binding in iron coordination complexes: toward spinswitching chemosensors. J. Am. Chem. Soc., 131: 32-33.
27. Enamullah, M., Hasegawa, M., Fukuda, Y., Linert, W., Hoshi, T. (2002). Synthesis, characterization and spincrossover behaviors of [Co(hydroxycarboxylato)(triphos)] complexes. Bull. Chem. Soc. Jpn., 75: 2449-2453.
28. Weber, B., Kaps, E. S., Obel, J., Achterhold, K., Parak, F. G. (2008). Synthesis and characterization of a dinuclear iron(II) spin crossover complex with wide hysteresis. Inorg. Chem., 47: 10779-10787.
29. Charbonnière, L. J., Williams, A. F., Piguet, C., Bernardinelli, G., Rivara-Minten, E. (1998). Structural, magnetic, and electrochemical properties of dinuclear triple helices: comparison with their mononuclear analogues. Chem. Eur. J., 4: 485-493.
30. Doukov, T., Li, H., Sharma, A., Martell, J. D., Soltis, S. M., Silverman, R. B., Poulos, T. L. (2011). Temperaturedependent spin crossover in neuronal nitric oxide synthase bound with the heme-coordinating thioether inhibitors. J. Am. Chem. Soc., 133: 8326-8334.
31. 4Py) and related complexes in aqueous media. Inorg. Chem., 51: 900-913.
32. Goodman, M. A., Nazarenko, A. Y., Casavant, B. J., Li, Z., Brennessel,W.W., DeMarco, M. J., Long, G., Goodman, M. S. (2012). Tris(5-methylpyrazolyl)methane: synthesis and properties of its iron(II) complex. Inorg. Chem., 51: 1084-1093.
33. Hain, S. K., Heinemann, F. W., Gieb, K., Mueller, P., Hoerner, G., Grohmann, A. (2010). On the spin behaviour of iron(II)-dipyridyltriazine complexes and their performance as thermal and photonic spin switches. Eur. J. Inorg. Chem, 221-232.
34. 2 in the low-spin and in the high-spin states. J. Phys. Chem. Lett., 1: 1830-1835.
35. Min, K. S., DiPasquale, A. G., Rheingold, A. L., White, H. S., Miller, J. S. (2009). Observation of redox-induced electron transfer and spin crossover for dinuclear cobalt and iron complexes with the 2,5-di-tert-butyl-3,6-dihydroxy-1,4-benzoquinonate bridging ligand. J. Am. Chem. Soc., 131: 6229-6236.
36. Pritchard, R., Barrett, S. A., Kilner, C. A., Halcrow, M. A. (2008). The influence of ligand conformation on the thermal spin transitions in iron(III) saltrien complexes. Dalton Trans, 3159-3168.
37. Telfer, S. G., Bocquet, B., Williams, A. F. (2001). Thermal spin crossover in binuclear iron(II) helicates: negative cooperativity and a mixed spin state in solution. Inorg. Chem., 40: 4818-4820.
38. Gandolfi, C., Moitzi, C., Schurtenberger, P., Morgan, G. G., Albrecht, M. (2008). Improved cooperativity of spinlabile iron(III) centers by self-assembly in solution. J. Am. Chem. Soc., 130: 14434-14435.
39. Martinho, P. N., Ortin, Y., Gildea, B., Gandolfi, C., McKerr, G., O'Hagan, B., Albrecht, M., Morgan, G. G. (2012). Inducing hysteretic spin crossover in solution. Dalton Trans., 41: 7461-7463.
40. Schlamp, S., Thoma, P., Weber, B. (2012). New octahedral, head-tail iron(II) complexes with spin crossover properties. Eur. J. Inorg. Chem, 2759-2768.
41. Coronado, E., Galán-Mascarós, J. R., Monrabal-Capilla, M., García-Martínez, J., Pardo-Ibáñez, P. (2007). Bistable spin-crossover nanoparticles showing magnetic thermal hysteresis near room temperature. Adv. Mater., 19: 1359-1361.
42. Galán-Mascarós, J. R., Coronado, E., Forment-Aliaga, A., Monrabal-Capilla, M., Pinilla-Cienfuegos, E., Ceolin, M. (2010). Tuning size and thermal hysteresis in bistable spin crossover nanoparticles. Inorg. Chem., 49: 5706-5714.
43. 2 nanoparticles showing synergy between core spin crossover and shell luminescence properties. Angew. Chem. Int. Ed., 50: 3290-3293.
44. Schweinfurth, D., Weisser, F., Bubrin, D., Bogani, L., Sarkar, B. (2011). Cobalt complexes with "click"-derived functional tripodal ligands: spin crossover and coordination ambivalence. Inorg. Chem., 50: 6114-6121.
45. 4]. J. Am. Chem. Soc., 122: 2272-2278.
46. 2+ [L = 2,6-di(pyrazol-1-yl)pyridine]. J. Chem. Soc. Dalton Trans, 548-554.
47. Lazar, H. Z., Forestier, T., Barrett, S. A., Kilner, C. A., Létard, J.-F., Halcrow, M. A. (2007). Thermal and lightinduced spin-crossover in salts of the heptadentate complex [tris(4-{pyrazol-3-yl}-3-aza-3-butenyl)amine]iron(II). Dalton Trans, 4276-4285.
48. 2O. Chem. Eur. J., 11: 5721-5734.
49. Hasegawa, Y., Kume, S., Nishihara, H. (2009). Reversible light-induced magnetization change in an azobenzeneattached pyridylbenzimidazole complex of iron(II) at room temperature. Dalton Trans, 280-284.
50. Rudd, D. J., Goldsmith, C. R., Cole, A. P., Stack, T. D. P., Hodgson, K. O., Hedman, B. (2005). X-ray absorption spectroscopic investigation of the spin-transition character in a series of single-site perturbed iron(II) complexes. Inorg. Chem., 44: 1221-1229.
51. 2 in solution (btpa = N,N,N⇌,N⇌-Tetrakis(2-pyridylmethyl)-6,6⇌-bis(aminomethyl)-2,2⇌-bipyridine). Inorg. Chem., 40: 134-139.
52. 2. Dalton Trans. 40: 944-950.
53. 2+ SCO complexes. Eur. J. Inorg. Chem, 1249-1254.
54. 4]2 in different solvents-a dramatic stabilisation of the low-spin state in water. Dalton Trans., 40: 12021-12024.
55. Turner, J. W., Schultz, F. A. (2001). Solution characterization of the iron(II) bis(1,4,7-triazacyclononane) spinequilibrium reaction. Inorg. Chem. 40: 5296-5298.
56. 3+/2+ complexes (tacn = 1,4,7-triazacyclononane; M = Cr, Mn, Fe, Co, Ni). J. Am. Chem. Soc., 131: 6189-6197.
57. Hitomi, Y., Higuchi, M., Minami, H., Tanaka, T., Funabiki, T. (2005). Tuning of spin crossover equilibrium in catecholatoiron(III) complexes by supporting ligands. Chem. Commun, 1758-1760.
58. Meredith, M. B., Crisp, J. A., Brady, E. D., Hanusa, T. P., Yee, G. T., Pink, M., Brennessel, W. W., Young, V. G. jr. (2008). Tunable spin-crossover behavior in polymethylated bis(indenyl)chromium(II) complexes: the significance of benzo-ring substitution. Organometallics, 27: 5464-5473.
59. 4)2 in solution. Eur. J. Inorg. Chem, 72-76.
60. Goldsmith, C. R., Jonas, R. T., Cole, A. P., Stack, T. D. P. (2002). A spectrochemical walk: single-site perturbation within a series of six-coordinate ferrous complexes. Inorg. Chem., 41: 4642-4652.
61. 5, and X-= monodentate anion. Inorg. Chem., 46: 7285-7293.
62. White, N. G., Feltham, H. L. C., Gandolfi, C., Albrecht, M., Brooker, S. (2010). Towards Langmuir-Blodgett films of magnetically interesting materials: solution equilibria in amphiphilic iron(II) complexes of a triazole-containing ligand. Dalton Trans., 39: 3751-3758.
63. Thies, S., Bornholdt, C., Köhler, F., Sönnichsen, F. D., Näther, C., Tuczek, F., Herges, R. (2010). Coordinationinduced spin crossover (CISCO) through axial bonding of substituted pyridines to nickel-porphyrins: σ-donor versus π-acceptor effects. Chem. Eur. J., 16: 10074-10083.
64. Thies, S., Sell, H., Schuett, C., Bornholdt, C., Näther, C., Tuczek, F., Herges, R. (2011). Light-induced spin change by photodissociable external ligands: a new principle for magnetic switching of molecules. J. Am. Chem. Soc., 133: 16243-16250.
65. Venkataramani, S., Jana, U., Dommaschk, M., Sönnichsen, F. D., Tuczek, F., Herges, R. (2011). Magnetic bistability of molecules in homogeneous solution at room temperature. Science, 331: 445-448.
66. III spin-crossover complexes with photoisomerizable ligands: experimental and theoretical studies on the ligand-driven light-induced spin change effect. Eur. J. Inorg. Chem, 2776-2783.
67. Ono, K., Yoshizawa, M., Akita, M., Kato, T., Tsunobuchi, Y., Ohkoshi, S., Fujita, M. (2009). Spin crossover by encapsulation. J. Am. Chem. Soc., 131: 2782-2783.
68. II bridged by 4-substituted 1,2,4-triazoles carrying alkyl tails. New J. Chem., 25: 144-150.
69. Halder, G. J., Kepert, C. J., Moubaraki, B., Murray, K. S., Cashion, J. D. (2002). Guest-dependent spin crossover in a nanoporous molecular framework material. Science, 298: 1762-1765.
70. Neville, S. M., Halder, G. J., Chapman, K.W., Duriska, M. B., Southon, P. D., Cashion, J. D., Létard, J.-F., Moubaraki, B., Murray, K. S., Kepert, C. J. (2008). Single-crystal to single-crystal structural transformation and photomagnetic properties of a porous iron(II) spin-crossover framework. J. Am. Chem. Soc., 130: 2869-2876.
71. Nihei, M., Han, L. Q., Oshio, H. (2007). Magnetic bistability and single-crystal-to-single-crystal transformation induced by guest desorption. J. Am. Chem. Soc., 129: 5312-5313.
72. Quesada, M., de la Peña-O'Shea V. A., Aromí, G., Geremia, S., Massera, C., Roubeau, O., Gamez, P., Reedijk, J. (2007). A molecule-based nanoporous material showing tuneable spin-crossover behavior near room temperature. Adv. Mater., 19: 1397-1402.
73. König, E. (1991). Nature and dynamics of the spin-state interconversion in metal complexes. Struct. Bonding, 76: 51-152.
74. Alberto, M. E., Mazzone, G., Russo, N., Sicilia, E. (2010). The mutual influence of non-covalent interactions in π-electron deficient cavities: the case of anion recognition by tetraoxacalix[2]arene[2]triazine. Chem. Commun., 46: 5894-5896.
75. Hostettler, M., Törnroos, K. W., Chernyshov, D., Vangdal, B., Bürgi, H.-B. (2004) Challenges in engineering spin crossover: structures and magnetic properties of six alcohol solvates of iron(II) tris(2-picolylamine) dichloride. Angew. Chem. Int. Ed., 43: 4589-4594.
76. Maeda, Y., Suzuki, M., Hirose, S., Hayami, S., Oniki, T., Sugihara, S. (1998). Effects of the encapsulation of alkali ions into iron(III) complexes with a macrocyclic ring on magnetic properties. Bull. Chem. Soc. Jpn., 71: 2837-2843.
77. Hauser, A. (2004). Ligand field theoretical considerations, in: Gütlich, P., Goodwin, H. A. (Eds) Spin Crossover in Transition Metal Compounds I. Top. Curr. Chem., 233: 49-58.
78. Zhang,W., Zhao, F., Liu, T., Yuan, M.,Wang, Z. M., Gao, S. (2007). Spin crossover in a series of iron(II) complexes of 2-(2-alkyl-2H-tetrazol-5-yl)-1,10-phenanthroline: effects of alkyl side chain, solvent, and anion. Inorg. Chem. 2007, 46, 2541-2555.
79. 4 Ligand)L] complexes. Inorg. Chem., 46: 4079-4089.
80. Me = tris[2-{[(2-methylimidazol-4-yl)methylidene]amino}ethyl]amine). Chem. Eur. J., 12: 4536-4549.
81. Goodwin, H. A. (2004). Spin crossover in iron(II) tris(diimine) and bis(terimine) systems, in: Gütlich, P., Goodwin, H. A. (Eds) Spin Crossover in Transition Metal Compounds I. Top. Curr. Chem., 233: 59-90.
82. 2 (X = F, Cl, Br, I): comparison of experimental results with those derived from density functional theory calculations. Chem. Eur. J., 12: 7421-7432.
83. 2 spin transitions in iron(II) and iron(III) complexes of 2,2⇌-bi-2-imidazoline and related ligands. J. Chem. Soc. Dalton Trans., 7: 1492-1497.
84. Yoder, J. C., Roth, J. P., Gussenhoven, E. M., Larsen, A. S., Mayer, J. M. (2003). Electron and hydrogen-atom self-exchange reactions of iron and cobalt coordination complexes. J. Am. Chem. Soc., 125: 2629-2640.
85. Robinson, M. A., Busch, D. H., Curry, J. D. (1963). Complexes derived from strong field ligands. XVII. Electronic spectra of octahedral nickel(II) complexes with ligands of the α-diimine and closely related classes. Inorg. Chem., 2: 1178-1181.
86. Ni, Z., Shores, M. P. (2010). Supramolecular effects on anion-dependent spin-state switching properties in heteroleptic iron(II) complexes. Inorg. Chem., 49: 10727-10735.
87. Kubik, S. (2010). Anion recognition in water. Chem. Soc. Rev., 39: 3648-3663.
88. Mannel-Croise, C., Meister, C., Zelder, F. (2010). "Naked-eye" screening of metal-based chemosensors for biologically important anions. Inorg. Chem., 49: 10220-10222.
89. Vallejos, S., Estévez, P., García, F. C., Serna, F., de la Peña, J. L., García, J. M. (2010). Putting to work organic sensing molecules in aqueous media: fluorene derivative-containing polymers as sensory materials for the colorimetric sensing of cyanide in water. Chem. Commun., 46: 7951-7953.
90. Hoselton, M. A., Wilson, L. J., Drago, R. S. (1975). Substituent effects on the spin equilibrium observed with hexadentate ligands on iron(II). J. Am. Chem. Soc., 97: 1722-1729.
91. + cations. Dalton Trans, 4132-4142.
92. Halcrow, M. A. (2007). The spin-states and spin-transitions of mononuclear iron(II) complexes of nitrogen-donor ligands. Polyhedron, 26: 3523-3576.
93. Amendola, V., Boiocchi, M., Colasson, B., Fabbrizzi, L., Douton, M. J. R., Ugozzoli, F. (2006). A metal-based trisimidazolium cage that provides six C-H hydrogen-bond-donor fragments and includes anions. Angew. Chem. Int. Ed., 45: 6920-6924.
94. Klug, C. M., McDaniel, A. M., Fiedler, S. R., Schulte, K. A., Newell, B. S., Shores, M. P. (2012). Anion dependence in the spin-crossover properties of a Fe(II) podand complex. Dalton Trans., 41: 12577-12585.
95. Sawada, T., Fujita, M. (2010). AsingleWatson-CrickG·C base pair inwater: aqueous hydrogen bonds in hydrophobic cavities. J. Am. Chem. Soc., 132: 7194-7201.
96. Goetz, S., Kruger, P. E. (2006). A new twist in anion binding: metallo-helicate hosts for anionic guests. Dalton Trans, 1277-1284.
97. Pelleteret, D., Clérac, R., Mathonière, C., Harté, E., Schmitt, W., Kruger, P. E. (2009). Asymmetric spin crossover behaviour and evidence of light-induced excited spin state trapping in a dinuclear iron(II) helicate. Chem. Commun, 221-223.
98. Dorazio, S. J., Morrow, J. R. (2012). The development of iron(II) complexes as paraCEST MRI contrast agents. Eur. J. Inorg. Chem, 2006-2014.
99. Blakesley, D. W., Payne, S. C., Hagen, K. S. (2000). Spin-state variation in solid state and solution of mononuclear iron(II) 1,4,7-trimethyl-1,4,7-triazacyclonane complexes. Inorg. Chem., 39: 1979-1989.