Statistical Analysis of Copper(I) Iodide and Bis(Diphenylphosphino)alkane-Based Complexes and Coordination Polymers

The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging. This is the case for Ph₂P(CH₂)_mPPh₂ ligands (1 ≤ m ≤ 8) and CuX salts, particularly for X = I. This work endeavors a systematic statistical analysis combining studies in the literature and new data, mapping the nature of the resulting CuI aggregates with eight different diphoshphines in 2:1, 3:2, 1:1, 2:3, and 1:2 CuI:Ph₂P(CH₂)_mPPh₂ molar ratios as a function of m, which lead to either pure products or mixtures. Several trends are made relating stoichiometry and chain length to the CuI cluster formed (i.e., globular vs. quasi-planar). Four new X-ray structures were determined: [Cu₃I₂(L1)₃]I, Cu₃I₃(L2)₂, Cu₂I₂(L6)₂, and Cu₄I₄(L8)₂, where m is, respectively, 1, 2, 6, and 8, in which the Cu_xI_y central aggregates adopt triangular bipyramid, diamond, rhomboid, and cubane shaped motifs, respectively. Photophysical measurements assisted the establishment of trends considering the paucity of the crystallographic structures. During this study, it was also found that the 0D-complex Cu₂I₂(Ph₂P(CH₂)₅PPh₂)₂ exhibits thermally activated delayed fluorescence.