Experimental and Theoretical Study of Novel Luminescent Di-, Tri-, and Tetranuclear Copper Triazole Complexes

Abstract

A number of novel luminescent di-, tri-, and tetranuclear copper complexes have been synthesized in good yields using a modular ligand system based on triazole-phosphines. This kind of ligand is easily accessible through an improved one-pot synthesis that permits the facile introduction of various alkyl or aromatic substituents at the 1-, 4-, or 5-position of the triazole ring. X-ray crystallography revealed three different types of complexes: neutral di- and tetranuclear structures with C i symmetry, and a charged trinuclear structure posessing C 3 symmetry. A spectroscopic evaluation showed promising photoluminescence properties in terms of their potential use in organic light-emitting devices, with maxima in the range of 500–550 nm, depending on the substitution pattern of the triazole ligand used for the complexation. Experimental observations were complemented by density functional theory calculations of ground and excited states.

Bright Coppertunities: Multinuclear CuI Complexes with N–P Ligands and Their Applications

“…[19b] To prevent such behavior, bridging and chelating ligands may be employed. However, while many N-P ligands are known, [27] so far none of them gave planar, White-type complexes [Cu 2 X 2 (N-P) 2 ]. Instead, other structural motifs are often found.…”

[2.2]Paracyclophane–Triazolyl Monophosphane Ligands: Synthesis and Their Copper and Palladium Complexes

“…[4,5] Therefore, we chose to react equimolar quantities of ligand 3a and CuI as the metal source in dichloromethane (Scheme 4). Our group recently showed that copper complexes with triazolyl-phosphane ligands have interesting photoluminescence properties.…”

“…As is well known, phosphanebased molecules are ligands of choice in many different organometallic-catalyzed processes. [5] At this stage, our interest laid in the synthesis and study of similar structures that were additionally chiral, and this would possibly allow the formation of enantiopure metal complexes. [1] Following the reliable procedure of Sharpless for the synthesis of triazoles, [2] Zhang reported the first synthesis of the ClickPhos family of ligands [3] (1, Figure 1).…”

Synthesis, characterization, and photoluminescent studies of three-coordinate Cu(i)–NHC complexes bearing unsymmetrically-substituted dipyridylamine ligands

“…The details of the theoretical calculations are described in the ESI. † Despite the diverse range of functionals and basis sets used for copper complexes in literature that oen provide good results, [50][51][52][53] the functional sensitivity of TD-DFT, especially for CT systems, 54 requires their careful screening in the luminescence studies. Geometry optimization.…”