Nanoclusters of Dicyanocuprate(I) Anions in Aqueous Solutions: Investigating Cuprophilic Interactions

The oligomerization of cyanocuprate(I) ions in aqueous solutions lacking and containing alkali cyanide salts (NaCN/KCN) has been investigated by infrared, Raman, and low temperature luminescence spectroscopy. In solution metallophilic interactions between Cu(I) metal centers bind the ions together into ∼1D chains. The structure and luminescence assignment of these nanoclusters was determined using simple Group Theory and Density Functional Theory calculations. Measurements show that the presence of KCN and NaCN in solution drives oligomerization of CuCN2− ions to higher order nanoclusters. Calculations of dimer and trimer clusters with K+ and Na+ ions indicate that alkali metals favor the formation of linear clusters as opposed to those that are bent. These findings fill an important gap in the understanding of d10 cyanometallate oligomers given the prevalence of cyanocuprate(I) in metal‐organic frameworks. The oligomerization of dicyanocuprate(I) ions in aqueous solutions has been investigated by IR, Raman, and luminescence spectroscopy. Measurements show that the presence of KCN and NaCN in solution drives oligomerization of CuCN2− ions towards higher order nanoclusters. These findings fill an important gap in the understanding of d10 dicyanocuprate(I) given its prevalence in metal‐organic frameworks and previous work on dicyanoaurate(I)/‐argenante(I) analogs.