Cu₄I₄-cubane clusters based on 10-(aryl)phenoxarsines and their luminescence

Abstract

The synthesis, structural and photophysical characterization, and theoretical study of tetranuclear copper(i) cubane-type Cu4I4 clusters with different 10-(aryl)phenoxarsine ligands are presented.

Emission and Luminescent Vapochromism Control of Octahedral Cu4I4 Complexes by Conformationally Restricted P,N Ligands

“…Among various copper(I) structures tetranuclear complexes become promising candidates for the design of “stimuli‐responsive” emitters [27,35] . The tetranuclear complexes are represented by structures with the stair‐step, cubane‐like, and octahedral Cu 4 I 4 metal‐halide cores [36–45] …”

Platinum(II) Complexes with 10-(Aryl)phenoxarsines: Synthesis, Cis/Trans Isomerization, and Luminescence

“…29 In our recent paper, the application of 10-(aryl)phenoxarsines as structure-forming units for the construction of luminescent copper complexes was reported. 30 These types of benzofused ligands are air-stable compared to phosphine ligands 27,31,32 and have relatively rigid and bulky structures, which is very important for the design of luminescent complexes. 33 In this study, we report the synthesis of platinum dihalide complexes based on cyclic phenoxarsines.…”

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

“…[47,50] To check the "ligand as well as heavy-atom" effect on the photophysical properties of copper(I) complexes, Galimova and co-workers synthesized copper(I) complexes having a Cu 4 I 4 cubane core with 10-(aryl)phenoxarsine ligands (aryl = p-fluorophenyl (1), pethoxy phenyl (2), phenyl (3), m-fluorophenyl (4) and o-methoxy phenyl (5). [51] Treatments of CuI with 1-5 in 1 : 1 molar ratios in acetonitrile under ambient reaction conditions afforded complexes 6-10 (Scheme 2). In the molecular structures of 6, 7 and 10, each copper centre of the Cu 4 I 4 cubane core is connected via three bridging μ 3 -iodides, and 10-(aryl)phenoxarsine ligand occupied the fourth coordination site, thus giving a tetrahedral environment around each copper centre.…”

“…[71][72] The photophysical properties of platinum(II) complexes of ligands with flat aromatic groups were found to be significantly influenced by π À π stacking and intermolecular Pt•••Pt interactions. [73] Inspired by their previous work on the photophysical properties of copper(I) complexes of sterically hindered (10-(aryl)phenoxarsine) ligands, [51] Galimova and co-workers opined that the bulky ligands may prevent intermolecular π-π interactions that would deactivate excitons through nonradiative relaxation routes. The platinum(II) complexes of 10-(pchlorophenyl)phenoxarsine ( 27), 10-(p-tolyl)phenoxarsine ( 28), and 10-(phenyl)phenoxarsine (29) were synthesized, and their photophysical properties were studied.…”