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Section: 12 | Organic Magnets |
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John R. Rumble, ed., CRC Handbook of Chemistry and Physics, 103rd Edition (Internet Version 2022), CRC Press/Taylor & Francis, Boca Raton, FL.
If a specific table is cited, use the format: "Physical Constants of Organic Compounds," in CRC Handbook of Chemistry and Physics, 103rd Edition (Internet Version 2022), John R. Rumble, ed., CRC Press/Taylor & Francis, Boca Raton, FL.

ORGANIC MAGNETS

J. S. Miller

Magnetic ordering, e.g., ferromagnetism, like superconductivity, is a property of a solid, not of an individual molecule or ion, and very rarely occurs for organic compounds. In contrast to superconductivity, where all electron spins pair to form a perfect diamagnetic material, magnetic ordering requires unpaired electron spins; hence, superconductivity and ferromagnetism are mutually exclusive.

The vast majority of organic compounds are diamagnetic (i.e., all electron spins are paired). Relatively few, possess unpaired electrons and are paramagnetic (PM), i.e., they are oriented in random directions. Some organic solids, however, exhibit strong magnetic behavior and magnetically order as ferromagnets (FO), with all spins aligned in the same direction. In some cases the spins align in the opposite direction and compensate to form an antiferromagnet (AF). In other cases, these spins are not opposed to each other and do not compensate and lead to a canted antiferromagnet or weak ferromagnet (WF). If the number of spins that align in one direction differs from the number of spins that align in the opposite direction, the spins cannot compensate and a ferrimagnet (FI) results. Metamagnets (MM) are antiferromagnets in which all the spins become aligned like a ferromagnet in an applied magnetic field. Above the ordering or critical temperature, Tc, all magnets are paramagnets (PM). Organic magnets all possess electron spins in p-orbitals, but these may be in conjunction with metal ion-based spins.

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Summary of the Critical Temperature, Tc, Saturation Magnetization, Ms, Coercive Field, Hcr, and Remanent Magnetization, Mr, for Selected Organic-Based Magnets



MagnetTypeTc/KMs/A m-1Hcr/TMr/A m-1
α-1,3,5,7-Tetramethyl-2,6-diazaadamantane-N,N’-doxylFO1.4848,300<0.00001
β-2-(4’-Nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-1-oxyl-3-N-oxideFO0.622,3000.00008 <200
{FeIII[C5(CH3)5]2}[TCNE]FO4.837,6000.102,300
{MnIII[C5(CH3)5]2}[TCNE]FO8.858,2000.123,700
{CrIII[C5(CH3)5]2}[TCNE]FO3.6546,300
α-{FeIII[C5(CH3)5]2}[TCNQ]MM2.5534,200
β-{FeIII[C5(CH3)5]2}[TCNQ]FO3.021,600
Tanol subarateMM0.3820,700
NCC6F4CN2S2WF35.5450.00009
MnII(hfac)2NITC2H5FI7.839,4000.0327,600
MnII(hfac)2NIT(i-C3H8)FI7.642,400<0.0005<420
[Mn(hfac)2]3[{ON[C6H3(t-C(CH3)3]2NO]2}FI4624,400
[MnTPP][TCNE].2C6H5CH3FI1318,4002.410,300
V[TCNE]x.yCH2Cl2(x ~ 2;y ~ 0.5)FI~40028,2000.0015 - 0.0061,650
Mn[TCNE]x.yCH2Cl2(x ~ 2;y ~ 0.5)FI7552,0000.002270
Fe[TCNE]x.yCH2Cl2(x ~ 2;y ~ 0.5)FI9746,3000.233
Co[TCNE]x.yCH2Cl2(x ~ 2;y ~ 0.5)FI4422,0000.65


List of Symbols and Abbreviations

chemical structure    chemical structure    chemical structure    chemical structure    chemical structure    chemical structure    chemical structure    chemical structure    chemical structure   chemical structure      chemical structure

References

  1. Miller, J. S. and Epstein, A. J., Angew. Chem. Internat. Ed., 33, 385, 1994. [https://doi.org/10.1002/anie.199403851]
  2. Chiarelli, R., Rassat, A., Dromzee, Y., Jeannin, Y., Novak, M. A., and Tholence, J. L., Phys. Scrip., T49, 706, 1993. [https://doi.org/10.1088/0031-8949/1993/T49B/055]
  3. Kinoshita, M., Jap. J. Appl. Phys., 33, 5718, 1994. [https://doi.org/10.1143/JJAP.33.5718]
  4. Gatteschi, D., Adv. Mat., 6, 635, 1994. [https://doi.org/10.1002/adma.19940060903]
  5. Miller, J. S. and Epstein, A. J., J. Chem. Soc., Chem. Commun., 1319, 1998. [https://doi.org/10.1039/a800922h]
  6. Broderick, W. E., Eichorn, D. M., Lu, X., Toscano, P. J., Owens, S. M. and Hoffman, B. M., J. Am. Chem. Soc., 117, 3641, 1995. [https://doi.org/10.1021/ja00117a045]
  7. Banister, A. J., Bricklebank, N., Lavander, I., Rawson, J., Gregory, C. I., Tanner, B. K., Clegg, W. J., Elsegood, M. R., and Palacio, F., Angew. Chem. Internat. Ed., 35, 2533, 1996. [https://doi.org/10.1002/anie.199625331]
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