The local structures of the new phosphorus chalcogenide – copper iodide coordination compounds (CuI)P4Se4, (CuI)2P8Se3, (CuI)3P4Se4, and (CuI)3P4S4 are investigated using comprehensive 63Cu, 65Cu, and 31P magic angle spinning NMR techniques. Peak assignments are proposed on the basis of homo- and heteronuclear indirect spin–spin interactions, available from lineshape analysis and/or two-dimensional correlation spectroscopy. In particular, the 31P-63,65Cu scalar coupling constants have been extracted from detailed lineshape simulations of the 31P resonances associated with the Cu-bonded P atoms. In addition, the RNνn pulse symmetry concept of Levitt and coworkers has been utilized for total through-bond correlation spectroscopy (TOBSY) of directly-bonded phosphorus species. The resonance assignments obtained facilitate a discussion of the 31P and 63,65Cu NMR Hamiltonian parameters in terms of the detailed local atomic environments. Analysis of the limited data set available for this group of closely related compounds offers the following conclusions: (1) bonding of a special phosphorus site in a given P4Xn
(X = S, Se) molecule to Cu+ ions shifts the corresponding 31P NMR signal upfield by about 50 ppm relative to the uncomplexed molecule, (2) the magnitude of the corresponding scalar 31P-63,65Cu spin–spin coupling constant tends to decrease with increasing Cu–P distance, and (3) the 63,65Cu nuclear electric quadrupolar coupling constants appear to be weakly correlated with the shear strain parameter specifying the degree of local distortion present in the four-coordinated [CuI2P2] and [CuI3P] environments. Overall, the results illustrate the power and potential of advanced solid state NMR methodology to provide useful structural information in this class of materials.