Luminescent complexes of heavy metals such as iridium, platinum, and ruthenium play an important role in photocatalysis and energy conversion applications as well as organic light-emitting diodes (OLEDs). Achieving comparable performance from more–earth-abundant copper requires overcoming the weak spin-orbit coupling of the light metal as well as limiting the high reorganization energies typical in copper(I) [Cu(I)] complexes. Here we report that two-coordinate Cu(I) complexes with redox active ligands in coplanar conformation manifest suppressed nonradiative decay, reduced structural reorganization, and sufficient orbital overlap for efficient charge transfer. We achieve photoluminescence efficiencies >99% and microsecond lifetimes, which lead to an efficient blue-emitting OLED. Photophysical analysis and simulations reveal a temperature-dependent interplay between emissive singlet and triplet charge-transfer states and amide-localized triplet states.

Singlet fission is a process in which a singlet exciton converts into two triplet excitons. To investigate this phenomenon, we synthesized two covalently linked 5-ethynyl-tetracene (ET) dimers with differing degrees of intertetracene overlap: BET-X, with large, cofacial overlap of tetracene π-orbitals, and BET-B, with twisted arrangement between tetracenes exhibits less overlap between the tetracene π-orbitals. The two compounds were crystallographically characterized and studied by absorption and emission spectroscopy in solution, in PMMA and neat thin films. The results show that singlet fission occurs within 1 ps in an amorphous thin film of BET-B with high efficiency (triplet yield: 154%). In solution and the PMMA matrix the S1 of BET-B relaxes to a correlated triplet pair (1)(T1T1) on a time scale of 2 ps, which decays to the ground state without forming separated triplets, suggesting that triplet energy transfer from (1)(T1T1) to a nearby chromophore is essential for producing free triplets. In support of this hypothesis, selective excitation of BET-B doped into a thin film of diphenyltetracene (DPT) leads to formation of the (1)(T1T1) state of BET-B, followed by generation of both DPT and BET-B triplets. For the structurally cofacial BET-X, an intermediate forms in <180 fs and returns to the ground state more rapidly than BET-B. First-principles calculations predict a 2 orders of magnitude faster rate of singlet fission to the (1)(T1T1) state in BET-B relative to that of crystalline tetracene, attributing the rate increase to greater coupling between the S1 and (1)(T1T1) states and favorable energetics for formation of the separated triplets.

A systematic study is presented on the physical and photophysical properties of isoelectronic and isostructural Cu, Ag, and Au complexes with a common amide (N-carbazolyl) and two different carbene ligands (i.e., CAAC = (5R,6S)-2-(2,6-diisopropylphenyl)-6-isopropyl-3,3,9-trimethyl-2-azaspiro­[4.5]­decan-2-ylidene, MAC = 1,3-bis­(2,6-diisopropylphenyl)-5,5-dimethyl-4-keto-tetrahydropyridylidene). The crystal structures of the (carbene)­M(I)(N-carbazolyl) (MCAAC) and (MAC)­M(I)(N-carbazolyl) (MMAC) complexes show coplanar carbene and carbzole ligands and C–M–N bond angles of ∼180°. The electrochemical properties and energies for charge transfer (CT) absorption and emission compounds are not significantly affected by the choice of metal ion. All six of the (carbene)­M­(Cz) complexes examined here display high photoluminescence quantum yields of 0.8–1.0. The compounds have short emission lifetimes (τ = 0.33–2.8 μs) that fall in the order Ag < Au < Cu, with the lifetimes of (carbene)­Ag­(Cz) roughly a factor of 10 shorter than for (carbene)­Cu­(Cz) complexes. Detailed temperature-dependent photophysical measurements (5–325 K) were carried out to determine the singlet and triplet emission lifetimes (τfl and τph, respectively) and the energy difference between the singlet and triplet excited state, ΔE S1–T1. The τfl values range between 20 and 85 ns, and the τph values are in the 50–200 μs regime. The emission at room temperature is due exclusively to E-type delayed fluorescence or TADF (i.e., ). The emission rate at room temperature is fully governed by ΔE S1–T1, with the silver complexes giving ΔE S1–T1 values of 150–180 cm–1 (18–23 meV), whereas the gold and copper complexes give values of 570–590 cm–1 (70–73 meV).

No abstract

The bioinspired incorporation of pendant proton donors into transition metal catalysts is a promising strategy for converting environmentally deleterious CO2 to higher energy products. However, the mechanism of proton transfer in these systems is poorly understood. Herein, we present a series of cobalt complexes with varying pendant secondary and tertiary amines in the ligand framework with the aim of disentangling the roles of the first and second coordination spheres in CO2 reduction catalysis. Electrochemical and kinetic studies indicate that the rate of catalysis shows a first-order dependence on acid, CO2, and the number of pendant secondary amines, respectively. Density functional theory studies explain the experimentally observed trends and indicate that pendant secondary amines do not directly transfer protons to CO2, but instead bind acid molecules from solution. Taken together, these results suggest a mechanism in which noncooperative pendant amines facilitate a hydrogen-bonding network that enables direct proton transfer from acid to the activated CO2 substrate.