The Influence of Aryl Substituents on the Supramolecular Structures and Photoluminescence of Cyclic Trinuclear Pyrazolato Copper(I) Complexes

Cyclic trinuclear complexes with group 11 metal (I) ions are fascinating and important to coordination chemistry. One of the ligands known to form these cyclic trinuclear complexes is pyrazolate, which is a bridging ligand that coordinates many transition metal ions in a Npz–M–Npz linear mode (Npz = pyrazolyl nitrogen atom). In these group 11 metal (I) ions, copper is the most abundant metal. Therefore, polynuclear Copper(I) complexes are very important in this field. The cyclic trinuclear Copper(I) complex [Cu(3,5-Ph2pz)]3 (3,5-Ph2pz– = 3,5-diphenyl-1-pyrazolate anion) was reported in 1988 as a landmark complex, but its photoluminescence properties have hitherto not been described. In this study, we report the photoluminescence and two different polymorphs of [Cu(3,5-Ph2pz)]3 and its derivative [Cu(3-Me-5-Phpz)]3 (3-Me-5-Phpz– = 3-metyl-5-phenyl-1-pyrazale anion). The substituents in [Cu(3-Me-5-Phpz)]3 cause smaller distortions in the solid-state structure and a red-shift in photoluminescence due to the presence of intermolecular cuprophilic interactions.

Regulating near-infrared region to visible-light emission by adjusting cuprophilic interactions for blue light-excited phosphors

Luminescent copper(I)-based clusters have attracted intensive attention in solid-state lighting. However, rationally regulating the luminescence performance through accurate structural control remains a challenge. Herein, three structurally different hexanuclear copper(I) nanoclusters...

A solid state highly emissive Cu(i) metallacycle: promotion of cuprophilic interactions at the excited states

The supramolecular synthesis of an original thermochromic metal-rich Cu(i) metallacycle (quantum yield 72% at RT) is reported. Important geometrical changes reinforcing cuprophilic interactions are calculated at the excited states.

An unusual coordination polymer containing Cu+ions and featuring possible Cu...Cu `cuprophilic' interactions: poly[di-μ-chlorido-(μ4-3,5-diaminobenzoato-κ4O:O′:N:N′)tricopper(I)(3Cu—Cu)]

Compounds containing copper(I) are of interest for their role in biological processes. The nature of short (< ∼3.2 Å) Cu...Cu contacts within these compounds has been debated, being either described as weakly attractive (bonding) `cuprophilic' interactions, or simply as short metal–metal distances constrained by ligand geometry or largely ionic in nature. The title three-dimensional Cu+-containing coordination polymer, [Cu3(C7H7N2O2)Cl2]n, was formed from thein situreduction of CuCl2in the presence of 3,5-diaminobenzoic acid and KOH under hydrothermal conditions. Its complex crystal structure contains ten distinct CuIatoms, two of which lie on crystallographic inversion centres. The copper coordination geometries include near-linear CuOCl and CuN2, T-shaped CuOCl2and distorted tetrahedral CuOCl3groups. Each CuIatom is also associated with two adjacent metal atoms, with Cu...Cu distances varying from 2.7350 (14) to 3.2142 (13) Å; if all these are regarded as `cuprophilic' interactions, then infinite [\overline{1}01] zigzag chains of CuIatoms occur in the crystal. The structure is consolidated by N—H...Cl hydrogen bonds.

Cuprophilic interactions in highly luminescent dicopper(i)–NHC–picolyl complexes – fast phosphorescence or TADF?

Cuprophilic interactions can greatly enhance the radiative rate constants via either exceptionally fast phosphorescence or TADF, and thus present a design motif for highly efficient CuI-based emitters.