Comparison of Nuclear Spin Relaxation of H2O@C60 and H2@C60 and Their Nitroxide Derivatives.
The successful synthesis of H2O@C60 makes possible the study of magnetic interactions of an isolated water molecule in a geometrically well-defined hydrophobic environment. Comparisons are made between the T1 values of H2O@C60 and the previously studied H2@C60 and their nitroxide derivatives. The value of T1 is approximately six times longer for H2O@C60 than for H2@C60 at room temperature, is independent of solvent viscosity or polarity, and increases monotonically with decreasing temperature, implying that T1 is dominated by the spin-rotation interaction. Paramagnetic nitroxides, either attached covalently to the C60 cage or added to the medium, produce strikingly similar T1 enhancements for H2O@C60 and H2@C60 that are consistent with through-space interaction between the internal nuclear spins and the external electron spin. This indicates that it should be possible to apply to the endo-H2O molecule the same methodologies for manipulating the ortho and para spin isomers that have proven successful for H2@C60.
†Department of Chemistry, Columbia University, New York, New York 10027, United States.
Yongjun
Y
Li
†Department of Chemistry, Columbia University, New York, New York 10027, United States.
Judy Y-C
JY
Chen
†Department of Chemistry, Columbia University, New York, New York 10027, United States.
Xuegong
X
Lei
‡Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
Ronald G
RG
Lawler
§Institute for Chemical Research, Kyoto University, Kyoto 611-0011, Japan.
Yasujiro
Y
Murata
∥Department of Environmental and Biological Chemistry, Fukui University of Technology, Gakuen, Fukui 910-8505, Japan.
Koichi
K
Komatsu
†Department of Chemistry, Columbia University, New York, New York 10027, United States.
Nicholas J
NJ
Turro
H2@C60; H2O@C60; Host@guest; endofullerene; fullerene derivatives; fullerene nitroxides; proton relaxation