Modeling Electron-Transfer Degradation of Organic Light-Emitting Devices.

The operational lifetime of organic light-emitting devices (OLEDs) is governed primarily by the intrinsic degradation of the materials. Therefore, a chemical model capable of predicting the operational stability is highly important. Here, a degradation model for OLEDs that exhibit thermally activated delayed fluorescence (TADF) is constructed and validated. The degradation model involves Langevin recombination of charge carriers on hosts, followed by the generation of a polaron pair through reductive electron transfer from a dopant to a host exciton as the initiation steps. The polarons undergo spontaneous decomposition, which competes with ultrafast recovery of the intact materials through charge recombination. Electrical and spectroscopic investigations provide information about the kinetics of each step in the operation and degradation of the devices, thereby enabling the building of mass balances for the key species in the emitting layers. Numerical solutions enable predictions of temporal decreases of the dopant concentration in various TADF emitting layers. The simulation results are in good agreement with experimental operational stabilities. This research disentangles the chemical processes in intrinsic electron-transfer degradation, and provides a useful foundation for improving the longevity of OLEDs.

Conformation-dependent degradation of thermally activated delayed fluorescence materials bearing cycloamino donors.

Organic light-emitting devices (OLEDs) containing organic molecules that exhibit thermally activated delayed fluorescence (TADF) produce high efficiencies. One challenge to the commercialization of the TADF OLEDs that remains to be addressed is their operational stability. Here we investigate the molecular factors that govern the stability of various archetypal TADF molecules based on a cycloamino donor-acceptor platform. Our results reveal that the intrinsic stability depends sensitively on the identity of the cycloamino donors in the TADF compounds. The rates and photochemical quantum yields of the degradation are positively correlated with the operation lifetimes of the devices. Our research shows that the stability is governed by the conformeric heterogeneity between the pseudo-axial and pseudo-equatorial forms of the cycloamino donor. Spontaneous bond dissociation occurs in the former (i.e., the pseudo-axial form), but the cleavage is disfavored in the pseudo-equatorial form. These findings provide valuable insights into the design of stable TADF molecules.

Monocycloplatinated Solvento Complex Displays Turn-on Ratiometric Phosphorescence Responses to Histamine.

The study of biological histamine (HA) requires probes capable of ratiometric photoluminescence detection of HA. We discovered that a monocycloplatinated complex having two solvento ligands ([Pt(2-(2-naphthyl)quinolinate)(NCCH3)2]ClO4) could produce ratiometric phosphorescence responses to HA in aerated aqueous solutions buffered to pH 7.4. The HA response was characterized with a hypsochromic shift of an emission peak wavelength from 635 to 567 nm. The corresponding phosphorescence intensity ratio (i.e., I567 nm/ I635 nm) increased from 0.26 to 1.90. Spectroscopic and spectrometric investigations indicated an occurrence of spontaneous displacement of the labile CH3CN ligands with HA. An independently prepared HA adduct supported this notion. The ratiometric phosphorescence responses to HA were highly tolerant to other biological stimuli, including changes in pH and the presence of biometals and biological Lewis bases such as amino acids, nucleosides, biothiols, neurotransmitters, and small molecular metabolites. Of note was the high selectivity toward HA over common biological ligands, including histidine, cysteine, and homocysteine, which was ascribed to tighter HA binding. Our phosphorescence measurements employing Boc-protected derivatives of HA suggested that the bis-chelate motif involving imidazolyl and terminal amino groups was crucial for eliciting the ratiometric phosphorescence signaling. Finally, the bioimaging utility of the HA probe was validated using RAW 264.7 macrophages that were exogenously supplemented with HA or stimulated with thapsigargin to enrich intracellular HA. Ratiometric phosphorescence imaging microscopy experiments demonstrated the ability of the probe for monitoring intracellular HA uptake. In addition, photoluminescence lifetime imaging microscopy techniques could be applied for visualization of HA within the RAW 264.7 cells, because the HA binding elongated the photoluminescence lifetime. Our study demonstrated the promising utility of inner-sphere interactions of phosphorescent Pt(II) complexes for detection of biological HA.

Degradation of blue-phosphorescent organic light-emitting devices involves exciton-induced generation of polaron pair within emitting layers.

Degradation of organic materials is responsible for the short operation lifetimes of organic light-emitting devices, but the mechanism by which such degradation is initiated has yet to be fully established. Here we report a new mechanism for degradation of emitting layers in blue-phosphorescent devices. We investigate binary mixtures of a wide bandgap host and a series of novel Ir(III) complex dopants having N-heterocyclocarbenic ligands. Our mechanistic study reveals the charge-neutral generation of polaron pairs (radical ion pairs) by electron transfer from the dopant to host excitons. Annihilation of the radical ion pair occurs by charge recombination, with such annihilation competing with bond scission. Device lifetime correlates linearly with the rate constant for the annihilation of the radical ion pair. Our findings demonstrate the importance of controlling exciton-induced electron transfer, and provide novel strategies to design materials for long-lifetime blue electrophosphorescence devices.

Photocatalytic function of the B12 complex with the cyclometalated iridium(iii) complex as a photosensitizer under visible light irradiation.

A visible light induced three-component catalytic system with the cobalamin derivative (B12) as a catalyst, the cyclometalated iridium(iii) complex (Irdfppy, Irppy, Irpbt and [Ir{dF(CF3)ppy}2(dtbpy)]PF6) as a photosensitizer and triethanolamine as an electron source under N2 was developed. This catalytic system showed a much higher catalytic efficiency than the previous catalytic system using [Ru(ii)(bpy)3]Cl2 as the photosensitizer for the dechlorination reaction of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT). Noteworthy is the fact that the remarkable high turnover number (over ten thousand) based on B12, which ranks at the top among the reported studies, was obtained when Irdfppy was used as a photosensitizer. This photocatalytic system was also successfully applied to the B12 enzyme-mimic reaction, i.e., the 1,2-migration of the phenyl group of 2-bromomethyl-2-phenylmalonate. The plausible reaction mechanism was proposed, which involved two quenching pathways, an oxidative quenching pathway and a reductive quenching pathway, to be responsible for the initial electron transfer of the excited-state photosensitizers during the DDT dechlorination reaction. Transient photoluminescence experiments revealed that the oxidative quenching of the photosensitizer dominated over the reductive quenching pathway.

Visible light-driven photogeneration of hydrogen sulfide.

The combined use of a singlet oxygen photosensitizer and 1,3-diarylisobenzothiophene enables efficient generation of hydrogen sulfide under visible light illumination.

Coreactant Strategy for the Photoredox Catalytic Generation of Trifluoromethyl Radicals under Low-Energy Photoirradiation.

Photoredox catalysis has emerged as a valuable alternative to dark-state catalysis. For the full potential of photoredox catalysis to be utilized, it is imperative to make use of low-energy photons in photoinduced radical processes. We have demonstrated that the use of oxalate as a coreactant provides a useful principle for the photocatalytic production of trifluoromethyl radicals (•CF3) from CF3I upon green or red LED photoirradiation of narrow-bandgap photocatalysts. The photocatalytic cycle involves a radical anion of carbon dioxide (CO2(•-)) as a reductant for CF3I, which is generated through photoinduced oxidative decarboxylation of oxalate. Electrochemical characterizations and steady-state and transient photophysical investigations were performed to reveal that there are two photoinduced electron-transfer pathways for oxalate-mediated •CF3 generation.