Relativistic modulation of supramolecular halogen/copper interactions and phosphorescence in Cu(i) pyrazolate cyclotrimers

Described herein are the synthesis, structure, and photophysics of the iodo-substituted cyclic trinuclear copper(i) complex, Cu-3[4-I-3,5-(CF3)(2)Pz](3) supported by a highly-fluorinated pyrazolate in comparison with its previously reported 4-Br/4-Cl analogues. The crystal structure is stabilised by multiple supramolecular interactions of Cu3MIDLINE HORIZONTAL ELLIPSISI and hydrogen/halogen bonding. The photophysical properties and supramolecular interactions are investigated experimentally/computationally for all three 4-halo complexes vis-a-vis relativistic effects.

Automated summary

This study explores the synthesis, structure, and photophysics of a cyclic trinuclear copper(i) complex with iodine substitution, Cu-3[4-I-3,5-(CF3)(2)Pz](3), in comparison with previously reported complexes containing 4-Br/4-Cl groups. The crystal structure is stabilized by various supramolecular interactions, including Cu3MIDLINE HORIZONTAL ELLIPSISI and hydrogen/halogen bonding. Experimental and computational investigations are conducted to study the photophysical properties and supramolecular interactions of all three 4-halo complexes in relation to relativistic effects.