ABSTRACT
Luminescent metal complexes based on earth abundant elements are a valuable target to substitute 4d/5d transition metal complexes as triplet emitters in advanced photonic applications. Whereas CuI complexes have been thoroughly investigated in the last two decades for this purpose, no structure-property-relationships for efficient luminescence involving triplet excited states from ZnII complexes are established. Herein, we report on the design of monomeric carbene zinc(II) dithiolates (CZT) featuring a donor-acceptor-motif that leads to highly efficient thermally activated delayed fluorescence (TADF) with for ZnII compounds unprecedented radiative rate constants kTADF =1.2×106 â s-1 at 297â K. Our high-level DFT/MRCI calculations revealed that the relative orientation of the ligands involved in the ligand-to-ligand charge transfer (1/3 LLCT) states is paramount to control the TADF process. Specifically, a dihedral angle of 36-40° leads to very efficient reverse intersystem-crossing (rISC) on the order of 109 â s-1 due to spin-orbit coupling (SOC) mediated by the sulfur atoms in combination with a small ΔES1-T1 of ca. 56â meV.
ABSTRACT
The sterically demanding N-heterocyclic carbene ITr (N,N'-bis(triphenylmethyl)imidazolylidene) was employed for the preparation of novel trigonal zinc(II) complexes of the type [ZnX2(ITr)] [X = Cl (1), Br (2), and I (3)], for which the low coordination mode was confirmed in both solution and solid state. Because of the atypical coordination geometry, the reactivity of 1-3 was studied in detail using partial or exhaustive halide exchange and halide abstraction reactions to access [ZnLCl(ITr)] [L = carbazolate (4), 3,6-di-tert-butyl-carbazolate (5), phenoxazine (6), and phenothiazine (7)], [Zn(bdt)(ITr)] (bdt = benzene-1,2-dithiolate) (8), and cationic [Zn(µ2-X)(ITr)]2[B(C6F5)4]2 [X = Cl (9), Br (10), and I (11)], all of which were isolated and structurally characterized. Importantly, for all complexes 4-11, the trigonal coordination environment of the ZnII ion is maintained, demonstrating a highly stabilizing effect due to the steric demand of the ITr ligand, which protects the metal center from further ligand association. In addition, complexes 1-3 and 8-11 show long-lived luminescence from triplet excited states in the solid state at room temperature, according to our photophysical studies. Our quantum chemical density functional theory/multireference configuration interaction (DFT/MRCI) calculations reveal that the phosphorescence of 8 originates from a locally excited triplet state on the bdt ligand. They further suggest that the phenyl substituents of ITr are photochemically not innocent but can coordinate to the electron-deficient metal center of this trigonal complex in the excited state.
ABSTRACT
Combined density functional theory and multireference configuration interaction methods including spin-orbit interactions have been employed to investigate the photophysical properties and deactivation pathways of a zinc diimine dithiolate complex involving the phenanthroline derivative bathocuproine and the dianionic dithiosquarate as chelating ligands. Zn(batho)(dtsq) is one of the few luminescent zinc complexes for which triplet emission had been reported in the solid state [Gronlund, P. Inorg. Chim. Acta 1995, 234, 13-18]. Because of the high dipole moment of the complex in the electronic ground state, ligand-to-ligand charge-transfer (LLCT) states experience strong hypsochromic shifts in polar media, while ligand-centered (LC) states are nearly unaffected. Rate constants for the thermally activated upconversion of the TLLCT population to the SLLCT state are promising due to a small singlet-triplet energy gap and the participation of the sulfur in the electronic excitation, but the TLLCT state is not the lowest-lying excited triplet state in ethanol solution. In addition to the TLLCT electronic structure, TLC(batho)' and TLC(dtsq) ππ* excitations form minima on the T1 potential energy surface. The SLLCT luminescence is expected to be quenched at the nanosecond time scale by the dark TLC(dtsq)ππ* state. Moreover, a TLC(dtsq)σπ* state has been identified, which leads to degradation of the compound. In mildly polar media, the dark triplet LC states are energetically inaccessible and the lowest excited singlet and triplet states clearly exhibit an LLCT character. However, their mutual spin-orbit coupling is reduced to the extent that reverse intersystem crossing is not very likely at room temperature. While Zn(diimine)(dithiolate) complexes continue to be perceived as an interesting substance class with potential application as emitters in electroluminescent devices, the particular Zn(batho)(dtsq) complex is not considered suitable for that purpose.
