π-Extended Ligands in Two-Coordinate Coinage Metal Complexes

Abstract

Two-coordinate carbene-M I -amide (cMa, M I = Cu, Ag, Au) complexes have emerged as highly efficient luminescent materials for use in a variety of photonic applications due to their extremely fast radiative rates through thermally activated delayed fluorescence (TADF) from an interligand charge transfer (ICT) process. A series of cMa derivatives was prepared to examine the variables that affect the radiative rate, with the goal of understanding the parameters that control the radiative TADF process in these materials. We find that blue-emissive complexes with high photoluminescence efficiencies (Φ PL > 0.95) and fast radiative rates (k r = 4 × 10 6 s −1 ) can be achieved by selectively extending the π-system of the carbene and amide ligands. Of note is the role played by the increased separation between the hole and electron in the ICT excited state. Analysis of temperature-dependent luminescence data and theoretical calculations indicate that the hole−electron separation exerts a primary effect on the energy gap between the lowest-energy singlet and triplet states (ΔE ST ) while keeping the radiative rate for the singlet state relatively unchanged. This interpretation provides guidelines for the design of new cMa derivatives with even faster radiative rates in addition to those with slower radiative rates and thus extended excited state lifetimes.Article pubs.acs.org/JACS

Photoactive Copper Complexes: Properties and Applications

“…Notably, OLEDs based on these complexes were found to be highly efficient and stable. Furthermore, an extensive combined experimental and in silico study of carbene-metal-amide complexes based on coinage metals, including copper, was carried out to determine the impact that the size of the π-system on both ligands has on the photophysical properties of complexes . This parameter enabled a fine-tuning of the singlet-triplet energy gap without affecting the radiative rate from the singlet state, allowing for faster emission desirable for OLEDs applications.…”

Correction to “Highly Efficient Photo- and Electroluminescence from Two-Coordinate Cu(I) Complexes Featuring Nonconventional N-Heterocyclic Carbenes”

“…The ZFS values for several other (carbene)­M­(Cz) complexes, listed here in Table , are uniformly in the range of 7–16 cm –1 for these linear, 2-coordinate complexes. The reason for the error in our previous ZFS value, quoting directly from page 17923 of our recent paper, is given below.…”

“…[Note: In the above quoted text “present results” and “Supporting Information” refer to ref and the values given in the tables below; refs 4e,f cited in the passage are DOIs 10.1021/jacs.9b03657 and 10.1021/jacs.8b12397. ]…”

Correction to “ ‘Quick-Silver’ from a Systematic Study of Highly Luminescent, Two-Coordinate, d10 Coinage Metal Complexes

“…Note that the CAAC ligand used for the derivatives in Table is substituted with an adamantly group instead of the menthyl group used in the original publication. The reason for the error in our previous ZFS value, quoting directly from page 17923 of our recent paper, is given below.…”

“…[Note: In the above quoted text “present results” and “Supporting Information” refer to ref and the values given in the table below; refs 4e,f cited in the passage are DOIs 10.1021/jacs.9b03657 and 10.1021/jacs.8b12397. ]…”