Three-coordinated boron-11 chemical shifts in borates.
نویسندگان
چکیده
Despite the importance of (11)B nuclear magnetic resonance (NMR) in structural studies of borate glasses, no clear means of correlating NMR parameters with the number of nonbridging oxygens on three-coordinate boron has been demonstrated. In this work, a series of anhydrous, polycrystalline, binary borates has been examined by (11)B magic-angle spinning (MAS) NMR to obtain precise measurements of their three-coordinate boron isotropic chemical shifts. The shifts generally increase with the replacement of bridging oxygens by nonbridging oxygens, ranging from 14.6 ppm in crystalline B(2)O(3) to 22.5 ppm in magnesium orthoborate. The underlying physical basis for this trend is satisfactorily accounted for by considering second neighbor effects using bond valence sums. These data are supportive of a structural model for B(2)O(3) glass in which 72% of the boron atoms are in rings. High-field MAS NMR experiments (B(0) = 18.8 T) indicate that the boron shielding is anisotropic, with greater anisotropy measured for three-coordinate borons possessing one or two nonbridging oxygens, than for those with zero or three nonbridging oxygens.
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ورودعنوان ژورنال:
- Inorganic chemistry
دوره 40 24 شماره
صفحات -
تاریخ انتشار 2001