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Article Dans Une Revue Molecules Année : 2023

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

Léo Boivin
Daniel Fortin
Pierre D. Harvey

Résumé

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 CuxIy 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.

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Chimie
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hal-04327489 , version 1 (06-12-2023)

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Léo Boivin, Adrien Schlachter, Daniel Fortin, Christophe Lescop, Pierre D. Harvey. Statistical Analysis of Copper(I) Iodide and Bis(Diphenylphosphino)alkane-Based Complexes and Coordination Polymers. Molecules, 2023, Molecules, 28 (23), pp.7781. ⟨10.3390/molecules28237781⟩. ⟨hal-04327489⟩
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