We have investigated the electronndash;nuclear double resonance (ENDOR) from frozen aqueous solutions of65Cu++(imidazole)4,65Cu++(imidazolendash;15N)4, and65Cu++(imidazolendash;Dn)4, wheren= 1, 2, 3, and 4 for selectively deuterated imidazole. We have observed ENDOR associated with the imidazole protons and the two imidazole nitrogens. The selective deuteration has allowed us to attempt identification of the weakly coupled protons responsible for the ENDOR spectrum, and a comparison of the overall line shape of that spectrum taken at two extreme points of the EPR spectrum suggests that some of the imidazole planes are tilted with respect to the plane of the complex. The ENDOR arising from the nitrogen nearest the copper is primarily isotropic withA(gperp;) = 41.6plusmn;1.5 MHz andA(gpar;) = 39.8plusmn;1.5 MHz. The resonance shows little structure and seems consistent with a picture that requires some inequivalence among the various imidazoles. The remote nitrogen ENDOR reveals both hyperfine and quadrupole effects with approximately isotropicA(14N) = 1.79 MHz,Qzprime;zprime;quest;0.360 MHz, andQxprime;xprime;yprime;xprime;quest;0.349 MHz. These values are in agreement with the results of the nuclear modulation effect lsqb;J. Chem. Phys. 69, 4921 (1978)rsqb;. The values for the quadrupole constants are thought to be accurate within 10percnt; and are the same as are found in free imidazole. It is also demonstrated that, in this instance, ENDOR and the nuclear modulation effect are complementary in that they have each provided different parts of the same hyperfine spectrum.
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