Anticandidal Cu(I) complexes with neocuproine and 1-(4-methoxyphenyl)piperazine based diphenylaminomethylphosphine: Is Cu-diimine moiety a pharmacophore?

The studies on metal complexes as potential antifungals are of growing interest because they may be the answer to increasingly effective defense mechanisms. Herein we present two new copper(I) iodide or thiocyanide complexes with 2,9-dimethyl-1,10-phenanthroline (dmp) and diphenylphosphine derivative of 1-(4-methoxyphenyl)piperazine (4MP): [CuI(dmp)4MP] (1-4MP) and [CuNCS(dmp)4MP] (2-4MP) - their synthesis, as well as structural and spectroscopic characteristics. Interestingly, while 4MP and its oxide derivative (4MOP) show a very low or no activity against all tested Candida albicans strains (MIC50 ≥ 200 µM against CAF2-1 - laboratory control strain, DSY1050 - mutant without transporters Cdr1, Cdr2, Mdr1; isogenic for CAF2-1, and fluconazole resistant clinical isolates), for 1-4MP and 2-4MP MIC50 values were 0.4 µM, independently on the complex and strain tested. Determination of the viability of NHDF-Ad (Normal Adult Human Dermal Fibroblasts) cell line treated with 1-4MP and 2-4MP showed that for both complexes there was only a 20% reduction in the concentration range » to 2 × MIC50 and the 70% at 4 × MIC50. Subsequently, the MLCT based luminescence of the complexes in aqueous media allowed to record the confocal micrographs of 1-4MP in the cells. The results show that it is situated most likely in the vacuoles (C. albicans) or lysosomes (NHDF-Ad).

TADF and X-ray Radioluminescence of New Cu(I) Halide Complexes: Different Halide Effects on These Processes.

A series of complexes [Cu2X2(Pic3PO)2] (X = Cl, Br, I) based on tris(pyridin-2-ylmethyl)phosphine oxide (Pic3PO) has been synthesized. At 298 K, these compounds exhibit thermally activated delayed fluorescence (TADF) of 1(M+X)LCT type with λmax varying from 485 to 545 nm, and quantum efficiency up to 54%. In the TADF process, the halide effect appears as the emission intensification and bathochromic shift of λmax in the following order X = I < Br < Cl. Upon X-ray irradiation, the title compounds emit radioluminescence, the emission bands of which have the same shape as those at TADF, thereby meaning a similar radiative excited state. By contrast to TADF, the halide effect in the radioluminescence is reversed: its intensity grows in the order X = Cl < Br < I, since heavier atoms absorb X-rays more efficiently. These findings essentially contribute to our knowledge about the halide effect in the photo- and radioluminescent Cu(I) halide emitters.

Tris(2-Pyridyl)Arsine as a New Platform for Design of Luminescent Cu(I) and Ag(I) Complexes.

The coordination behavior of tris(2-pyridyl)arsine (Py3As) has been studied for the first time on the example of the reactions with CuI, CuBr and AgClO4. When treated with CuI in CH2Cl2 medium, Py3As unexpectedly affords the scorpionate complex [Cu(Py3As)I]∙CH2Cl2 only, while this reaction in MeCN selectively leads to the dimer [Cu2(Py3As)2I2]. At the same time, the interaction of CuBr with Py3As exclusively gives the dimer [Cu2(Py3As)2Br2]. It is interesting to note that the scorpionate [Cu(Py3As)I]∙CH2Cl2, upon fuming with a MeCN vapor (r.t., 1 h), undergoes quantitative dimerization into the dimer [Cu2(Py3As)2I2]. The reaction of Py3As with AgClO4 produces complex [Ag@Ag4(Py3As)4](CIO4)5 featuring a Ag-centered Ag4 tetrahedral kernel. At ambient temperature, the obtained Cu(I) complexes exhibit an unusually short-lived photoluminescence, which can be tentatively assigned to the thermally activated delayed fluorescence of (M + X) LCT type (M = Cu, L = Py3As; X = halogen). For the title Ag(I) complexes, QTAIM calculations reveal the pronounced argentophilic interactions for all short Ag∙∙∙Ag contacts (3.209-3.313 Å).

New Approach toward Dual-Emissive Organic-Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals.

Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)3]2+ cations and various anionic [CuxIy](y-x)- clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn2+ ions (605-648 nm) and iodocuprate anions (480-728 nm). Noteworthily, the relative ratio of the emission bands, and hence a resulting emission chromaticity, can be tuned in a wide range through modification of cluster [CuxIy](y-x)- modules. The structural diversity, enhanced robustness, and up to 100% luminescence quantum yield make the designed materials promising phosphors for lighting and sensing applications.

Thiourea Dioxide Coupled with Trace Cu(II): An Effective Process for the Reductive Degradation of Diatrizoate.

Diatrizoate, a refractory ionic iodinated X-ray contrast media (ICM) compound, cannot be efficiently degraded in a complex wastewater matrix even by advanced oxidation processes. We report in this research that a homogeneous process, thiourea dioxide (TDO) coupled with trace Cu(II) (several micromoles, ubiquitous in some wastewater), is effective for reductive deiodination and degradation of diatrizoate at neutral pH values. Specifically, the molar ratio of iodide released to TDO consumed reached 2 under ideal experimental conditions. TDO eventually decomposed into urea and sulfite/sulfate. Based on the results of diatrizoate degradation, TDO decomposition, and Cu(I) generation and consumption during the TDO-Cu(II) reaction, we confirmed that Cu(I) is responsible for diatrizoate degradation. However, free Cu(I) alone did not work. It was proposed that Cu(I) complexes are actual reactive species toward diatrizoate. Inorganic anions and effluent organic matter negatively influence diatrizoate degradation, but by increasing the TDO dosage, as well as extending the reaction time, its degradation efficiency can still be guaranteed for real hospital wastewater. This reduction reaction could be potentially useful for in situ deiodination and degradation of diatrizoate in hospital wastewater before discharge into municipal sewage networks.

Solution-Processed OLEDs Based on Thermally Activated Delayed Fluorescence Copper(I) Complexes with Intraligand Charge-Transfer Excited State.

A new series of tetrahedral heteroleptic copper(I) complexes exhibiting efficient thermally-activated delayed fluorescence (TADF) in green to orange electromagnetic spectral regions has been developed by using D-A type N^N ligand and P^P ligands. Their structures, electrochemical, photophysical, and electroluminescence properties have been characterized. The complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 0.71 at room temperature in doped film and the lifetimes are in a wide range of 4.3-24.1 µs. Density functional theory (DFT) calculations on the complexes reveal the lowest-lying intraligand charge-transfer excited states that are localized on the N^N ligands. Solution-processed organic light emitting diodes (OLEDs) based on one of the new emitters show a maximum external quantum efficiency (EQE) of 7.96%.

Synthesis, Structures, and Photophysical Properties of Novel Four-Coordinate Cu(I) Complexes Supported by Chelating N-Heterocyclic Carbene Ligands.

Luminescent Cu(I) complexes are promising emitting materials for electroluminescent devices due to their low cost and abundant resources, as well as high emission efficiency. It is well-known that N-heterocyclic carbenes (NHCs) are excellent ligands for transition metal complexes. To investigate the photophysical properties of Cu(I)-NHC complexes, a series of new mononuclear four-coordinate Cu(I) complexes supported by the diphosphine ligand bis[2-(diphenylphosphino)phenyl]ether (POP) and the NHC ligands, consisting of imidazolylidene and pyrimidine units, were synthesized and fully characterized. To tune the photophysical properties of these Cu(I)-NHC complexes, the NHC ligands were attached with electron-withdrawing/donating groups (fluorine, chlorine, methyl and methoxyl) at the pyrimidine unit. All of these Cu(I)-NHC complexes adopt the typical distorted tetrahedral configuration. The electron-donating groups can lead to shorter Cu-N bond distances and longer Cu-C bond distances compared to the electron-withdrawing groups. Theoretical calculation results show that the highest occupied molecular orbitals are mainly distributed on the Cu(I) ion, POP, and carbene unit, while the lowest unoccupied molecular orbitals are mostly located on the pyrimidine unit of NHC ligands. The lowest energy electronic transitions of these Cu(I)-NHC complexes are mainly the metal-to-ligand charge transfer transition and ligand-to-ligand charge transfer transition. These Cu(I)-NHC complexes in solid state show tunable emissions from 530 to 618 nm with efficiencies of 0.5-38.1% at room temperature. The photophysical behaviors of these complexes at 298 and 50 K match well with the thermally activated delayed fluorescence (TADF) characteristics.

Photocatalytic CO2 Reduction Using Various Heteroleptic Diimine-Diphosphine Cu(I) Complexes as Photosensitizers.

The development of efficient redox-photosensitizers based on the earth-abundant metal ions as an alternative toward noble- and/or rare-metal based photosensitizers is very desirable. In recent years, heteroleptic diimine-diphosphine Cu(I) complexes have been well investigated as one of the most remarkable candidates because of their great potentials as efficient photosensitizers. Here, we investigated the effects of the structure of the diphosphine ligands on the photosensitizing abilities using a series of Cu(I) complexes bearing 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (dmpp) and various diphosphine ligands in order to explore the suitable structure for the photosensitizing reactions. The number of methylene chains between the two phosphorous atoms in the diphosphine ligands was systematically changed from two to four, and the relationship between the length of the carbon chains and the photosensitizing abilities were investigated by conducting photocatalytic CO2 reduction with the Cu(I) complexes as photosensitizers. Turnover frequencies of the CO2 reduction drastically increased with increasing the length of the carbon chains. The systematic study herein reported suggests that the large P-Cu-P angles should be one of the most important factors for enhancing the photosensitizing abilities.

Thermally Activated Delayed Fluorescence in CuI Complexes Originating from Restricted Molecular Vibrations.

The mechanism of thermally activated delayed fluorescence (TADF) in molecules in aggregated or condensed solid states has been rarely studied and is not well understood. Nevertheless, many applications of TADF emitters are strongly affected by their luminescence properties in the aggregated state. In this study, two new isomeric tetradentate CuI complexes which simultaneously show aggregation induced emission (AIE) and TADF characteristics are reported for the first time. We provide direct evidence that effectively restricting the vibrations of individual molecules is a key requisite for TADF in these two CuI complexes through in-depth photophysical measurements combined with kinetic methods, single crystal analysis and theoretical calculations. These findings should stimulate new molecular engineering endeavours in the design of AIE-TADF active materials with highly emissive aggregated states.

Cu(I) complexes of bis(methyl)(thia/selena) salen ligands: Synthesis, characterization, redox behavior and DNA binding studies.

Mononuclear cuprous complexes 1 and 2, [{CH3E(o-C6H4)CH=NCH2}2Cu]ClO4; E=S/Se, have been synthesized by the reaction of bis(methyl)(thia/selena) salen ligands and [Cu(CH3CN)4]ClO4. Both the products were characterized by elemental analysis, ESI-MS, FT-IR, 1H/13C/77Se NMR, and cyclic voltammetry. The complexes possess tetrahedral geometry around metal center with the N2S2/N2Se2 coordination core. Cyclic voltammograms of complexes 1 and 2 displayed reversible anodic waves at E1/2=+0.08V and +0.10V, respectively, corresponding to the Cu(I)/Cu(II) redox couple. DNA binding studies of both the complexes were performed applying absorbance, fluorescence and molecular docking techniques. Competitive binding experiment of complexes with ct-DNA against ethidium bromide is performed to predict the mode of binding. The results indicate the groove binding mode of complexes 1 and 2 to DNA. The binding constants revealed the strong binding affinity of complexes towards ct-DNA.

Balanced Dual Emissions from Tridentate Phosphine-Coordinate Copper(I) Complexes toward Highly Efficient Yellow OLEDs.

Dual emissive copper(I) halide complexes TTPPCuX (X = Cl, Br, I) with a triphosphine ligand and stable tetrahedral geometries are constructed, in which TTPPCuI successfully achieves the balanced dual thermally activated delayed fluorescence and phosphorescence (PH) emissions with PH fraction of 39% at ambient temperature, supporting the equal triplet exciton reallocation for the state-of-the-art device performance.

Synthesis and study on a series of phosphorescent Cu(I) complexes having sterically blocking ligands.

In this paper, we report six phosphorescent Cu(I) complexes with 1,10-phenanthroline-derived ligands and phosphorous ligands, including their synthesis, crystal structures, photophysical properties, and electronic nature. The Cu(I) center has a distorted tetrahedral geometry within the Cu(I) complexes. Theoretical calculation reveals that all emissions originate from triplet metal-to-ligand-charge-transfer excited state. It is found that the introduction of alkyl moieties into 2,9-positions of 1,10-phenanthroline is highly effective on restricting the geometric relaxation that occurs in excited states, which greatly enhances the photoluminescence (PL) performances, including PL quantum yield improvement, PL decay lifetime increase, and emission blue shift.