Assembly of Heterometallic AuICu2I2 Cores on the Scaffold of NPPN-Bridging Cyclic Bisphosphine

The row of metallocyclic dinuclear gold(I) complexes with cyclic diphosphines, namely, P-pyridylethyl-substituted 1,5-diaza-3,7-diphosphacyclooctanes, has been obtained. Further interaction of the dinuclear gold(I) complexes with copper(I) iodide gave the first examples of hexanuclear Au-I/Cu-I complexes containing two unusual trinuclear AuICu2I2 fragments. The structures of di- and hexanuclear complexes were confirmed by NMR spectroscopy, ESI mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. All of the obtained complexes are moderate emitters in the solid state. Dinuclear gold(I) complexes displayed a greenish emission with the maxima in the emission spectra at ca. 550 nm. The obtained hexanuclear heterobimetallic Au-I/Cu-I complexes are triplet solid-state blue emitters with the maximum in the emission spectra at 463 and 484 nm. According to the TD-DFT calculations, the observed emission of all studied complexes had a triplet origin and was caused by the (CC)-C-3 or (3)(MLCT) T-1 -> S-0 transitions for dinuclear and hexanuclear complexes, respectively.

Automated summary

In this study, dinuclear gold(I) complexes and hexanuclear Au-I/Cu-I complexes were synthesized, both of which exhibited luminescent properties in the solid state. The dinuclear gold(I) complexes displayed green emission with a maximum in the emission spectra at around 550 nm, while the obtained hexanuclear heterobimetallic Au-I/Cu-I complexes were triplet solid-state blue emitters with maximum emission spectra at 463 and 484 nm.