Initial conditions for carbon-13 MAS NMR 1D exchange involving chemically equivalent and inequivalent nuclei

Abstract

A major problem in dynamic 1D (13)C MAS NMR concerns the exchange between magnetically inequivalent, but chemically equivalent sites, whose signals are not resolved in the regular 1D spectrum. This difficulty may be overcome by properly preparing the initial nonequilibrium state of the spin system in the exchange experiments. In the present paper we discuss the advantages and limitations of several such experiments already in use and propose a new sequence, which we term SELDOM-ODESSA. Unlike the other 1D-exchange methods, this experiment yields pure absorption spectra that can more readily be analyzed quantitatively. The experiment is a hybrid comprising a SELDOM sequence, for selective excitation of one of the spinning sideband manifolds in the spectrum, followed by the ODESSA sequence, which induces alternate polarization in the excited sideband manifold. The evolution of the spectrum following this sequence provides information on both the exchange between congruent sites belonging to the same group of equivalent nuclei, and the exchange between inequivalent sites. Results are presented for a tropolone sample specifically enriched in carbon-13 at the carbonyl and hydroxyl sites. The dominant exchange mechanism in this sample involves spin diffusion. The various spin exchange processes in this sample, in the presence and absence of proton decoupling during the mixing time, are measured and discussed. Copyright 2000 Academic Press.