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 (1), Cbz (2), acac (3), Ph₂acac (4), Cp (5), and Cp* (6)) 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 1-6. Furthermore, 1-5 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)] (2) 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 k_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 2. 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 2, showing distinct antibunching as required for single-photon emitters.

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