Bis(salicylamidine) Ligands (FAlen): A Variant of Salen with "à la Carte" Denticity.

Ethylene- and phenylene-bridged bis(salicylamidine) ligands have been readily prepared from ethylene or phenylenediamine and iminium chloride derivatives generated in situ from N,N-dialkylsalicylamides. The former, in its diprotonated form (FAlenH2), reacts with AlMe3 to afford a zwitterionic dimethyldiphenoxyaluminate complex with the FAlen ligand monoprotonated and in a bidentate κ2O,O' fashion. A phenylene-bridged proligand behaves differently, yielding a neutral methylaluminum complex bearing a κ3O,N,O'-coordinated FAlen ligand. From these complexes, methyl anion abstraction with B(C6F5)3 or a reaction with Schrock's alcohol leads to the corresponding aluminum cationic or alkoxy complexes in which a κ4O,N,N',O'-coordination mode of the FAlen ligand is observed. X-ray diffraction studies of the proligands and of the complexes show that the amidine functions feature a trans configuration when the N-amidine atom is not coordinated to the metal and conversely a cis configuration when it is. Density functional theory calculations show that trans-cis isomerization of the amidine functions occurs upon coordination with the metal ion with very low energy barriers. They also confirm the intuition that the denticity of the FAlen ligands in the complexes is directly related to the electron richness of the metal ion. At last, FAlen Al complexes are used as initiators for the controlled ring-opening polymerization of rac-lactide to afford poly(lactic acid) with slight isotactic bias.

Excited-State Lifetime Modulation by Twisted and Tilted Molecular Design in Carbene-Metal-Amide Photoemitters.

Carbene-metal-amides (CMAs) are an emerging class of photoemitters based on a linear donor-linker-acceptor arrangement. They exhibit high flexibility about the carbene-metal and metal-amide bonds, leading to a conformational freedom which has a strong influence on their photophysical properties. Herein we report CMA complexes with (1) nearly coplanar, (2) twisted, (3) tilted, and (4) tilt-twisted orientations between donor and acceptor ligands and illustrate the influence of preferred ground-state conformations on both the luminescence quantum yields and excited-state lifetimes. The performance is found to be optimum for structures with partially twisted and/or tilted conformations, resulting in radiative rates exceeding 1 × 106 s-1. Although the metal atoms make only small contributions to HOMOs and LUMOs, they provide sufficient spin-orbit coupling between the low-lying excited states to reduce the excited-state lifetimes down to 500 ns. At the same time, high photoluminescence quantum yields are maintained for a strongly tilted emitter in a host matrix. Proof-of-concept organic light-emitting diodes (OLEDs) based on these new emitter designs were fabricated, with a maximum external quantum efficiency (EQE) of 19.1% with low device roll-off efficiency. Transient electroluminescence studies indicate that molecular design concepts for new CMA emitters can be successfully translated into the OLED device.

Highly efficient blue organic light-emitting diodes based on carbene-metal-amides.

Carbene-metal-amides are soluble and thermally stable materials which have recently emerged as emitters in high-performance organic light-emitting diodes. Here we synthesise carbene-metal-amide photoemitters with CF3-substituted ligands to show sky-blue to deep-blue photoluminescence from charge-transfer excited states. We demonstrate that the emission colour can be adjusted from blue to yellow and observe that the relative energies of charge transfer and locally excited triplet states influence the performance of the deep-blue emission. High thermal stability and insensitivity to aggregation-induced luminescence quenching allow us to fabricate organic light-emitting diodes in both host-free and host-guest architectures. We report blue devices with a peak external quantum efficiency of 17.3% in a host-free emitting layer and 20.9% in a polar host. Our findings inform the molecular design of the next generation of stable blue carbene-metal-amide emitters.

Carbene metal amide photoemitters: tailoring conformationally flexible amides for full color range emissions including white-emitting OLED.

Conformationally flexible "Carbene-Metal-Amide" (CMA) complexes of copper and gold have been developed based on a combination of sterically hindered cyclic (alkyl)(amino)carbene (CAAC) and 6- and 7-ring heterocyclic amide ligands. These complexes show photoemissions across the visible spectrum with PL quantum yields of up to 89% in solution and 83% in host-guest films. Single crystal X-ray diffraction and photoluminescence (PL) studies combined with DFT calculations indicate the important role of ring structure and conformational flexibility of the amide ligands. Time-resolved PL shows efficient delayed emission with sub-microsecond to microsecond excited state lifetimes at room temperature, with radiative rates exceeding 106 s-1. Yellow organic light-emitting diodes (OLEDs) based on a 7-ring gold amide were fabricated by thermal vapor deposition, while the sky-blue to warm-white mechanochromic behavior of the gold phenothiazine-5,5-dioxide complex enabled fabrication of the first CMA-based white light-emitting OLED.

Synthesis of copper(i) cyclic (alkyl)(amino)carbene complexes with potentially bidentate N

The reaction of (Me2L)CuCl with either NaS2CX [X = OEt, NEt2 or carbazolate (Cz)] or with 1,3-diarylguanidine, 1,3-diarylformamidine or thioacetaniline in the presence of KOtBu affords the corresponding S- or N-bound copper complexes (Me2L)Cu(S^S) 1-3, (Me2L)Cu(N^N) 4/5 and (Me2L)Cu(N^S) 6 (aryl = 2,6-diisopropylphenyl; Me2L = 2,6-bis(isopropyl)phenyl-3,3,5,5-tetramethyl-2-pyrrolidinylidene). The crystal structure of (Me2L)Cu(S2CCz) (3) confirmed the three-coordinate geometry with S^S chelation and perpendicular orientation of the carbene and S^S ligands. On heating 3 cleanly eliminates CS2 and forms (Me2L)CuCz. The N-bound complexes show strongly distorted T-shaped (4) or undistorted linear (5) geometries. On excitation with UV light the S-bound complexes proved non-emissive, while the guanidinato and formamidinato complexes are strongly phosphorescent, with excited state lifetimes in the range of 11-24 µs in the solid state. The conformationally flexible formamidinato complex 5 shows intense green-white phosphorescence with a solid-state quantum yield of >96%.

Gold(I)-Coumarin-Caffeine-Based Complexes as New Potential Anti-Inflammatory and Anticancer Trackable Agents.

Three new gold(I)-coumarin-based trackable therapeutic complexes and two non-trackable analogues have been synthesised and fully characterised. They all display anti-proliferative properties on several types of cancer cell lines, including those of colon, breast, and prostate. Two complexes displayed significant anti-inflammatory effects; one displayed pro-inflammatory behaviour; this highlights the impact of the position of the fluorophore on the caffeine scaffold. Additionally, the three coumarin derivatives could be visualised in vitro by two-photon microscopy.

Gold(i)-BODIPY-imidazole bimetallic complexes as new potential anti-inflammatory and anticancer trackable agents.

Two new gold(i)-BODIPY-imidazole based trackable therapeutic bimetallic complexes have been synthesized and fully characterized. They display strong antiproliferative properties on several types of cancers including colon, breast, and prostate and one of them presents a significant anti-inflammatory effect. Additionally, the two compounds could be visualised in vitro by confocal microscopy in the submicromolar range.

Water-soluble nickel-bis(dithiolene) complexes as photothermal agents.

The remarkable photothermal properties of pegylated nickel-bis(dithiolene) complexes in water can induce cell death under laser irradiation in the near infrared (NIR) region.

Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a "Smart" Probe Answer!

Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. The in vitro biological action of the gold complexes and the phosphonium derivative were investigated, and a preliminary in vivo study in healthy zebrafish larvae allowed us to evaluate gold complex biodistribution and toxicity. The different analyses carried out showed that these gold complexes were stable and behaved differently from phosphonium and auranofin, both in vitro and in vivo. Two-photon microscopy experiments demonstrated that the cellular targets of these gold complexes are not the same as those of the phosphonium analogue. Moreover, despite similar IC50 values in some cancer cell lines, gold complexes displayed a low toxicity in vivo, in contrast to the phosphonium salt. They are therefore suitable for future in vivo investigations.