Determination of J coupling constants between spin-1/2 and quadrupolar nuclei in inorganic solids from spin echo and refocused INEPT experiments: a case study on AlPO₄ berlinite.

A systematic study utilizing rotor-synchronized homonuclear ((31)P, (27)Al) and heteronuclear ({(31)P}(27)Al and {(27)Al}(31)P) spin echo, and {(27)Al}(31)P refocused INEPT experiments (employing soft pulses for selective excitation of the central transition for the quadrupolar (27)Al (I=5/2)) have been performed on AlPO(4) berlinite at 30 kHz MAS to better understand the J modulation behavior involving half-integer quadrupolar nuclei in solid materials with framework structure. Analyses of the J modulation on either the (27)Al or (31)P coherence in both the {(31)P}(27)Al and {(27)Al}(31)P spin echo experiments, and both periods of the refocused INEPT experiment yield consistent results for the (2)J(AlP) (Al-O-P) coupling constant (ca. 25 Hz). It is noted that the coupling of each (27)Al to four (31)P spins during the first ((27)Al) evolution period of the refocused INEPT, and the populations of (31)P coupled to different numbers (0-4) of (27)Al in the ± 1/2 Zeeman states during (31)P coherence evolution, which have been neglected in previous studies, must be taken into account for proper treatment. Analysis of J modulation on the spin ((27)Al) coupled to spin-1/2 nuclei in general gives more accurate results. Weak long-range homonuclear (4)J(PP) (P-O-Al-O-P) coupling was also observed from the (31)P spin echo and INADEQUATE experiments.