Solid-State NMR Connectivity Studies in Dipolarly Coupled Inorganic Networks: Crystal Structure and Site Assignments for the Lithium Polyphosphide LiP5

Structure and Vibrational Analyses of LiP15

“…The Li atoms are shifted from the starting positions towards the (2b)P and (3b)P sites (Figure 4a), and Li–(2b)P and Li–(3b)P distances of 2.59–2.70 Å are predicted. These values are consistent with those reported for Li 3 P4 [ d (Li–P) = 2.4414(2)–2.523(3) Å], LiP 7 7 [ d (Li–P) = 2.67–2.88 Å] and LiP 5 8 in the space group Pna 2 1 [ d (Li–P) = 2.525(3)–3.099(4) Å]. A pronounced anisotropy in the distribution of the Li–(2b)P distances can be observed; the long distances are 3.77 and 3.25 Å, whereas the short Li–(2b)P distances are 2.61 and 2.70 Å.…”

“…The most lithium‐rich phosphide, Li 3 P, consists of isolated P 3– ions,3,4 whereas molecular [P 7 3– ] units are present in Li 3 P 7 5. Whereas LiP6 and LiP 7 7 possess an anionic ∞ 1 [P – ] helical chain substructure, LiP 5 7,8 features a three‐dimensional network of phosphorus atoms. The title polyphosphide LiP 15 9 adds another facet to the structural diversity, as it features tubular ∞ 1 [P 15 – ] units that are comparable with the architecture of the strands found in violet and fibrous phosphorus allotropes 10,11…”

mP‐BaP3: A New Phase from an Old Binary System

“…In the case of mS ‐BaP 3 , the two 31 P isotropic shifts are located at −60 and −149 ppm, and integration of these isotropic peaks and their corresponding spinning sidebands yields a ratio of ∼1:2 that allows for unequivocal assignment of these peaks to the P1 and P2 crystallographic sites, respectively. The 31 P isotropic chemical shift of the twofold coordinated P2 site is within the range characteristic of P atoms with formal negative charge P 1− 29. The larger shielding of the P2 site compared to the threefold coordinated P1 site indicates the presence of Ba nearest neighbors plays an important role in controlling the chemical shifts of the phosphorus sites in these materials.…”

Zintl‐Ionen, Käfigverbindungen und intermetalloide Cluster der Elemente der 14. und 15. Gruppe

“…In den letzten 30 Jahren hat sich die Magic‐Angle‐Spinning(MAS)‐NMR‐Spektroskopie zu einem unverzichtbaren Werkzeug für die Strukturcharakterisierung insbesondere von amorphen oder fehlgeordneten Feststoffen entwickelt. Die 31 P‐MAS‐NMR‐Spektroskopie wird jedoch durch eine schlechte Auflösung aufgrund von 31 P‐ 31 P‐Dipol‐Dipol‐Wechselwirkungen beeinträchtigt, die sich selbst bei hohen Rotationsgeschwindigkeiten nicht herausmitteln 286…”

“…Das dreidimensionale kontinuierliche Netzwerk aus Phosphoratomen des [P 5 ] − ‐Anions in LiP 5 wurde mittels ein‐ und multidimensionaler NMR‐Spektroskopie eingehend untersucht. Die chemischen Verschiebungen liegen zwischen δ =−128 und δ =+2 ppm 286…”