Phosphorus(V) Nitrides: Preparation, Properties, and Possible Applications of New Solid State Materials with Structural Analogies to Phosphates and Silicates

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Abstract
With the synthesis of pure, stoichiometric, and crystalline phosphorus nitride P3N5 an essential for the systematic investigation of higher phosphorus nitrides has become available. By solid state reaction of P3N5 with Li3N and Ca3N2, respectively, the following ternary compounds have been synthesized and have been characterized by their crystal structures and properties: Li7PN4, Li12P3N9, Li10P4N10, LiPN2, and Ca2PN3. By defined heterogeneous ammonolyses of P3N5 the phosphorus nitride imides HPN2 and HP4N7 have been obtained. Sodalite-type phosphorus nitrides (e.g. M7-xH2x[P12N24]Z2-y; M=Fe, Co, Ni, Mn etc.; 0≤x≤2; Z=Cl, Br; 0≤y≤2) are accessible via reaction of HPN2 with metal chlorides MCl2. Silicon phosphorus nitride SiPN3 is obtained by ammonolysis of Cl3SiNPCl3 followed by pyrolysis in an ammonia stream. All phosphorus nitrides obtained so far contain PN4-tetrahedra as characteristic building units which may be interconnected by common vertices showing differing degrees of condensation. Practical applications of phosphorus nitrides as solid state electrolytes and pigments are discussed.

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