Phosphates are ubiquitous within the biologic and industrial materials fields, serving as essential energy storage vehicles and structural units . Phosphates have also recently been shown to exhibit liquid-like clusters in solution, presenting additional complexity to understanding the growth of phosphate-containing structures . The nonclassical nucleation of calcium phosphate clusters as the precursors to bone formation has been observed within seconds at concentrations which are only accessible to NMR enhanced by dissolution DNP , resulting in inadequate time for structural analysis. Sample vitrification and the extraction of the number of coupled 31 P nuclei at various early stage time points would allow for monitoring PNCs and the evolution of calcium phosphate phase formation. The feasibility of spin counting in vitrified solutions under DNP conditions for P species should be relevant to the many biological and chemical processes that use phosphate containing species as structural building blocks or energy sources. Our studies show the feasibility of DNP-enabled spin counting and can be expanded to any spin 2 system in the future. In the case of calcium phosphate, understanding the assembly and growth mechanism(s) of phosphate clusters is the first step in elucidating the structure and evolution of the various species formed. In this effort, the most rudimentary question is how many phosphorous atoms are correlated in the species formed along the phosphate nucleation growth pathway?