Cyclic (Amino)(aryl)carbenes Enter the Field of Chromophore Ligands: Expanded π System Leads to Unusually Deep Red Emitting Cu^I Compounds

Abstract

A series of copper(I) complexes bearing a cyclic (amino)(aryl)carbene (CAArC) ligand with various complex geometries have been investigated in great detail with regard to their structural, electronic, and photophysical properties. Comparison of [CuX(CAArC)] (X = Br (<b>1</b>), Cbz (<b>2</b>), acac (<b>3</b>), Ph₂acac (<b>4</b>), Cp (<b>5</b>), and Cp* (<b>6</b>)) with known Cu^I complexes bearing cyclic (amino)(alkyl), monoamido, or diamido carbenes (CAAC, MAC, or DAC, respectively) as chromophore ligands reveals that the expanded π-system of the CAArC leads to relatively low energy absorption maxima between 350 and 550 nm in THF with high absorption coefficients of 5-15 × 10³ M^-1 cm^-1 for <b>1</b>-<b>6</b>. Furthermore, <b>1</b>-<b>5</b> show intense deep red to near-IR emission involving their triplet excited states in the solid state and in PMMA films with λ^em_max = 621-784 nm. Linear [Cu(Cbz)(^DippCAArC)] (<b>2</b>) has been found to be an exceptional deep red (λ_max = 621 nm, ϕ = 0.32, τ_av = 366 ns) thermally activated delayed fluorescence (TADF) emitter with a radiative rate constant <i>k</i>_r of ca. 9 × 10⁵ s^-1, exceeding those of commercially employed Ir^III- or Pt^II-based emitters. Time-resolved transient absorption and fluorescence upconversion experiments complemented by quantum chemical calculations employing Kohn-Sham density functional theory and multireference configuration interaction methods as well as temperature-dependent steady-state and time-resolved luminescence studies provide a detailed picture of the excited-state dynamics of <b>2</b>. To demonstrate the potential applicability of this new class of low-energy emitters in future photonic applications, such as nonclassical light sources for quantum communication or quantum cryptography, we have successfully conducted single-molecule photon-correlation experiments of <b>2</b>, showing distinct antibunching as required for single-photon emitters.