Strongly Luminescent Tungsten Emitters with Emission Quantum Yields of up to 84 %: TADF and High-Efficiency Molecular Tungsten OLEDs.

Metal-TADF (thermally activated delayed fluorescence) emitters hold promise in the development of next generation light-emitting materials for display and lighting applications, examples of which are, however, largely confined to CuI and recently AuI , AgI , and AuIII emitters. Herein is described the design strategy for an unprecedented type of metal-TADF emitter based on inexpensive tungsten metal chelated with Schiff base ligand that exhibit high emission quantum yields of up to 56 % in solutions and 84 % in thin-film (5 wt % in 1,3-bis(N-carbazolyl)benzene, mCP) at room temperature. Femtosecond time-resolved emission (fs-TRE) spectroscopy and DFT calculations were undertaken to decipher the TADF properties. Solution-processed OLEDs fabricated with the W-TADF emitter demonstrated external quantum efficiency (EQE) and luminance of up to 15.6 % and 16890 cd m-2 , respectively.

Luminescent tungsten(vi) complexes as photocatalysts for light-driven C-C and C-B bond formation reactions.

The realization of photocatalysis for practical synthetic application hinges on the development of inexpensive photocatalysts which can be prepared on a large scale. Herein an air-stable, visible-light-absorbing photoluminescent tungsten(vi) complex which can be conveniently prepared at the gram-scale is described. This complex could catalyse photochemical organic transformation reactions including borylation of aryl halides, such as aryl chloride, reductive coupling of benzyl bromides for C-C bond formation, reductive coupling of phenacyl bromides, and decarboxylative coupling of redox-active esters of alkyl carboxylic acid with high product yields and broad functional group tolerance.

Strongly Luminescent Cyclometalated Gold(III) Complexes Supported by Bidentate Ligands Displaying Intermolecular Interactions and Tunable Emission Energy.

A series of charge-neutral AuIII complexes, which comprise a dicarbanionic C-deprotonated biphenyl ligand and bidentate ancillary ligands ([Au(C^C)(L^X)]; L^X=ß-diketonate and relatives (O^O), quinolinolate and relatives (N^O), and diphosphino (P^P) ligands), were prepared. All the complexes are emissive in degassed CH2 Cl2 solutions and in thin-film samples with Φem up to 18 and 35 %, respectively, except for 5 and 6, which bear (N^O)-type ancillary ligands. Variation of the electronic characteristics of the ß-diketonate ancillary ligand was demonstrated to be a viable route for tuning the emission color from blue-green (peak λem at ca. 466 nm for 1 and 2; 501 nm for 4 a and 4 b) to orange (peak λem at 585 nm for 3), in contrast to the common observations that the ancillary ligand has a negligible effect on the excited-state energy of the AuIII complexes reported in the literature. DFT/time-dependent (TD) DFT calculations revealed that the energies of the 3 ππ*(C^C) and the 3 ILCT(O^O) excited states (ILCT=intraligand charge transfer) switch in order on going from O^O=acetylacetonate (acac) to aryl-substituted ß-diketonate ligands. Solution-processed and vacuum-deposited organic light-emitting diode (OLED) devices of selected complexes were prepared. The vacuum-deposited OLED fabricated with 2 displays a sky-blue emission with a maximum external quantum efficiency (EQE) of 6.71 % and CIE coordinates of (0.22, 0.40). The crystal structures of 7 and 9 reveal short intermolecular AuIII ⋅⋅⋅AuIII contacts, with intermetal distances of 3.408 and 3.453 Å, respectively. DFT/TDDFT calculations were performed on 7 and 9 to account for the noncovalent interactions. Solid samples of 1, 3, and 9 exhibit excimeric emission at room temperature, which is rarely reported in AuIII complexes.

The interplay between fluorescence and phosphorescence with luminescent gold(i) and gold(iii) complexes bearing heterocyclic arylacetylide ligands.

The photophysical properties of a series of gold(i) [LAu(C[triple bond, length as m-dash]CR)] (L = PCy3 (1a-4a), RNC (5a), NHC (6a)) and gold(iii) complexes [Au(C^N^C)(C[triple bond, length as m-dash]CR)] (1b-4b) bearing heterocyclic arylacetylide ligands with narrow band-gap are compared. The luminescence of both series are derived from an intraligand transition localized on the arylacetylide ligand (ππ*(C[triple bond, length as m-dash]CR)) but 1a-3a displayed prompt fluorescence (τ PF = 2.7-12.0 ns) while 1b-3b showed mainly phosphorescence (τ Ph = 104-205 µs). The experimentally determined intersystem crossing (ISC) rate constants (k ISC) are on the order of 106 to 108 s-1 for the gold(i) series (1a-3a) but 1010 to 1011 s-1 for the gold(iii) analogues (1b-3b). DFT/TDDFT calculations have been performed to help understand the difference in the k ISC between the two series of complexes. Owing to the different oxidation states of the gold ion, the Au(i) complexes have linear coordination geometry while the Au(iii) complexes are square planar. It was found from DFT/TDDFT calculations that due to this difference in coordination geometries, the energy gap between the singlet and triplet excited states (ΔE ST) with effective spin-orbit coupling (SOC) for Au(i) systems is much larger than that for the Au(iii) counterparts, thus resulting in the poor ISC efficiency for the former. Time-resolved spectroscopies revealed a minor contribution (<2.9%) of a long-lived delayed fluorescence (DF) (τ DF = 4.6-12.5 µs) to the total fluorescence in 1a-3a. Attempts have been made to elucidate the mechanism for the origins of the DF: the dependence of the DF intensity with the power of excitation light reveals that triplet-triplet annihilation (TTA) is the most probable mechanism for the DF of 1a while germinate electron-hole pair (GP) recombination accounts for the DF of 2a in 77 K glassy solution (MeOH/EtOH = 4 : 1). Both 4a and 4b contain a BODIPY moiety at the acetylide ligand and display only 1IL(ππ*) fluorescence with negligible phosphorescence being observed. Computational analyses attributed this observation to the lack of low-lying triplet excited states that could have effective SOC with the S1 excited state.

Theoretical studies on the photophysical properties of luminescent pincer gold(iii) arylacetylide complexes: the role of π-conjugation at the C-deprotonated [C

We have performed theoretical analyses of the photophysical properties of a series of cyclometalated gold(iii) arylacetylide complexes, [(C^N^C)AuIIIC[triple bond, length as m-dash]CPh-4-OMe], with different extents of π-conjugation at the doubly C-deprotonated [C^N^C] ligand via replacement of one of the phenyl moieties in the non-conjugated CH^N^C ligand (1) by a naphthalenyl (2) or a fluorenyl moiety (3-exo and 3-endo; HCH^N^CH = 2,6-diphenylpyridine). Conforming to the conventional wisdom that extended π-conjugation imposes rigidity on the structure of the 3IL(ππ*(C^N^C)) excited state (IL = intraligand), the calculated Huang-Rhys factors for the 3IL → S0 transition follow the order: 1 > 2 > 3-exo ∼ 3-endo, which corroborates qualitatively the experimental non-radiative decay rate constants, k nr: 1 ≫ 2 > 3-exo, but not 3-endo. Density Functional Theory (DFT) calculations revealed that there is an additional triplet excited state minimum of 3LLCT character (LLCT = ligand-to-ligand charge transfer; 3[π(C[triple bond, length as m-dash]CPh-4-OMe) → π*(C^N^C)]) for complexes 1 and 3-endo. This 3LLCT excited state, possessing a large out-of-plane torsional motion between the planes of the C^N^C and arylacetylide ligands, has a double minimum anharmonic potential energy surface along this torsional coordinate which leads to enhanced Franck-Condon overlap between the 3LLCT excited state and the ground state. Together with the larger spin-orbit coupling (SOC) and solvent reorganization energy for the 3LLCT → S0 transition compared with those for the 3IL → S0 transition, the calculated k nr values for the 3LLCT → S0 transition are more than 690- and 1500-fold greater than the corresponding 3IL → S0 transition for complexes 1 and 3-endo respectively. Importantly, when this 3LLCT → S0 decay channel is taken into consideration, the non-radiative decay rate constant k nr could be reproduced quantitatively and in the order of: 1 ≫ 3-endo, 2 > 3-exo. This challenges the common view that the facile non-radiative decay rate of transition metal complexes is due to the presence of a low-lying metal-centred 3dd or 3LMCT excited state (LMCT = ligand-to-metal charge transfer). By analysis of the relative order of MOs of the chromophoric [C^N^C] cyclometalated and arylacetylide ligands, one may discern why complexes 1 and 3-endo have a low-lying 3LLCT excited state while 3-exo does not.

Metal-organic framework composites with luminescent gold(iii) complexes. Strongly emissive and long-lived excited states in open air and photo-catalysis.

The encapsulation of luminescent gold(iii) complexes by metal-organic frameworks (MOFs) lays the groundwork for new phosphorescent materials with activities that are not readily achieved by the host MOF materials or gold(iii) complexes alone. In this work, strong phosphorescence with lifetimes of up to ∼50 µs in open air at room temperature has been achieved by incorporation of cationic cyclometalated gold(iii) complexes into MOFs with anionic frameworks to form AuIII@MOFs. The AuIII@MOFs display solid state two-photon-induced phosphorescence. Photo-reduction of methyl viologen to the reduced radical was achieved inside AuIII@MOFs and in the presence of Et3N upon excitation at λ > 370 nm under ambient conditions. These AuIII@MOFs comprise a class of reusable and size-selective heterogeneous photo-catalysts for the aerobic oxidation of secondary amines to imines as well as five other reactions, including oxidative C-H functionalization under aerobic conditions.

Color tunable organic light-emitting devices with external quantum efficiency over 20% based on strongly luminescent gold(III) complexes having long-lived emissive excited states.

Gold(III) complexes supported by C-deprotonated fluorene-C^N^C ligands having high emission quantum yield up to 0.61 and long-lived emissive excited states are used as yellow emitters in color tunable PLEDs and OLEDs. High EQEs of 13.16% and 22.02% are achieved in the best PLED and OLED, respectively.