Organic spin clusters: Macrocyclic-macrocyclic polyarylmethyl polyradicals with very high spin S = 5-13

Journal of the American Chemical Society

Volumn 126, Issue 21, 2004, Pages 6608-6626

  Rajca, Andrzej ^a   Wongsriratanakul, Jirawat ^a   Rajca, Suchada ^a  

^a UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTIFERROMAGNETISM; FREE RADICALS; MAGNETIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; POLYETHERS; SOLUTIONS;

FERROMAGNETIC COUPLINGS; ORGANIC SPIN CLUSTERS; POLYRADICALS; TRIMERS;

SYNTHESIS (CHEMICAL);

CALIXARENE; FERROMAGNETIC MATERIAL; MACROCYCLIC COMPOUND; RADICAL; TETRAHYDROFURAN;

ACCELERATION; ARTICLE; MAGNETISM; NUCLEAR MAGNETIC RESONANCE; QUANTITATIVE ANALYSIS; STEREOISOMERISM; SYNTHESIS;

EID: 2542619025     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja031549b     Document Type: Article

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38. s point group.
39. 2-symmetric 11D.
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41. 1-symmetric 17 corresponds to the least polar cis/trans isomer 7A in ref 37.
42. 4v-symmetric tetrabromo-calix[4]-arene core 18 is described in refs 1 and 2.
43. For other examples of cyclostereoisomerism, see: Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994, 1176-1177.
44. 1H chemical shifts for both products are within 0.01 ppm at room temperature.
45. Our previous attempts to separate polyarylmethyl polyethers using either normal or reverse phase HPLC have not been successful. For selected chromatographic separations, silica is activated at 200 °C.
46. 15(OH).
47. 28 is about 10%.
48. W would be negligible, considering other sources of error.
49. gq < 1.10. The small angle neutron scattering (SANS) experiments and the data handling are described in Supporting Information.
50. Carlin, R. L. Magnetochemistry; Springer: Berlin, 1986.
51. For numerical fits of the M vs H/T data for pentadecaradical 2 at 1.8 K, using eq 1, moderate parameter dependence in the 0.67-0.89 range is found.
52. This near perfect generation of 22-radical 3 may be the result of a more extensive effort in its generation; only a subset of samples is reported.
53. sat (and χ(T), which are calculated on the basis of the weighed masses of polyethers. For 2 and 3, numerical fits to the percolation model, which include the mass of the polyether as a third variable parameter, are overparametrized; the fitted masses are typically greater (by 10-20%), compared to the weighed masses.
54. The downward turn in χT at H = 5000 Oe is caused by the paramagnetic saturation, as illustrated in Figure 11s, Supporting Information.