Phenylene Bridge Research Articles

Non-symmetrical 1,3,4-oxadiazole derivatives: Synthesis, characterization, and computational study of their optical properties

Applications in electronics and photonics have spurred research on new electronic and optical materials, including organic chromophores. In this work, we synthesized and characterized five compounds (4 of which novel) containing the 1,3,4-oxadiazole group. Four of the molecules contain one oxadiazole moiety connected on one side to a phenylene bridge and an aliphatic tail, while the other side terminates with either a thiophene or a pyridine group. The fifth molecule features an additional phenylene and oxadiazole group separating the core from its thiophene terminus. DFT calculations were used to investigate the photophysical properties of the molecules. The calculated excitation energy reflected well the trend observed in the UV–Vis spectra. The calculated first hyperpolarizability (β(0)) increased as the pyridine groups replaced the thiophenes. Extending the π-conjugated bridge did increase β in comparison to the shorter analog (both with the 2-thiophenyl end group), probably due to decreasing bandgap and excitation energy. Still, the highest β(0) found was for the compound containing the 4-pyridyl end group (Oxa-4-Py, 24.0 × 10−30 e.s.u.), suggesting that the appropriate end group might overcome the effect of extending π-conjugation.

Diamine Groups on the Surface of Silica Particles as Complex-Forming Linkers for Metal Cations

Novel spherically shaped organosilica materials with (propyl)ethylenediamine groups were obtained via a modified one-pot Stöber co-condensation method. The porosity of these materials was tuned with the controlled addition of three silica monomers acting as structuring agents (tetraethoxysilane and bridged silanes with ethylene and phenylene bridges). The morphologies and structures of the synthesized materials were studied by SEM, DRIFT spectroscopy, CHNS elemental analysis, low-temperature nitrogen adsorption-desorption, and electrokinetic potential measurements. Their sizes were in the range of 50 to 100 nm, depending on the amount of structuring silane used in the reaction. The degree of the particles' agglomeration determined the mesoporosity of the samples. The content of the (propyl)ethylenediamine groups was directly related with the amount of functional silane used in the reaction. The zeta potential measurements indicated the presence of silanol groups in bissilane-based samples, which added new active centers on the surface and reduced the activity of the amino groups. The static sorption capacities (SSCs) of the obtained samples towards Cu(II), Ni(II), and Eu(III) ions depended on the porosity of the samples and the spatial arrangement of the ethylenediamine groups; therefore, the SSC values were not always higher for the samples with the largest number of groups. The highest SSC values achieved were 1.8 mmolCu(II)/g (for ethylene-bridged samples), 0.83 mmolNi(II)/g (for phenylene-bridged samples), and 0.55 mmolEu(III)/g (for tetraethoxysilane-based samples).

The photophysical properties of sulfone-based TADF emitters in relation to their structural properties.

In this work, thermally activated delayed fluorescence (TADF) of a series of emitters with sulfone-based acceptor moieties was studied by density functional theory (DFT) methods. Sulfone derivatives were shown to be high performing TADF emitters over recent years. When discussing the TADF efficiency, various properties, such as the singlet-triplet energy gap (ΔEST), spin-orbit coupling (SOC) and the nature of states, stand out due to their roles in reverse intersystem crossing (RISC). Here, we mainly focused on three important structural parameters that affect the intersystem crossing (ISC) and RISC pathways and their efficiencies. These three parameters are: (1) the effect of meta- and para-conjugation, (2) the effect of rigid acceptor moieties and (3) the effect of the phenyl bridge on photophysical properties.

Synthesis, Molecular Docking, Dynamics, Quantum-Chemical Computation, and Antimicrobial Activity Studies of Some New Benzimidazole-Thiadiazole Hybrids.

In this study, some new compounds, which are 2-aminothiadiazole derivatives linked by a phenyl bridge to the 2-position of the benzimidazole ring, were designed and synthesized as antimicrobial agents. The structures of the compounds were elucidated by 1H and 13C NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis. The antifungal activities of the synthesized compounds were tested on Candida albicans, Candida krusei, Candida glabrata, and Candida parapsilosis. Compound 5f is more active against C. albicans and C. glabrata than standard fluconazole and varicanazole. Compounds were also evaluated for their counteracting activity against Gram-positive Escherichia coli, Serratia marcescens, Klebsiella pneumoniae, and Pseudomonas aeruginosa and Gram-negative Enterococcus faecalis, Bacillus subtilis, and Staphylococcus aureus. Compounds 5c and 5h had minimum inhibitory concentrations against E. faecalis close to that of the standard azithromycin. Molecular docking studies were performed against Candida species' 14-α demethylase enzyme. 5f was the most active compound against Candida species, which gave the highest docking interaction energy. The stabilities of compounds 5c and 5f with CYP51 were tested using 100 ns molecular dynamics simulations. According to the theoretical ADME calculations, the profiles of the compounds are suitable in terms of limiting rules. HOMO-LUMO analysis showed that 5h is chemically more reactive (represented with the lower ΔE = 3.432 eV) than the other molecules, which is compatible with the highest antibacterial activity result.

Linear, two- and four-armed pyridine-decorated thiazolo[5,4-d]thiazole fluorophores: Synthesis, photophysical study and computational investigation

A novel family of thiazolo[5,4-d]thiazole (TzTz) fluorophores having a general formula (py)n-π-TzTz-π-(py)n (n = 1 or 2, py = pyridine) is herein reported. The investigated compounds are decorated with alkoxy-substituted pyridine scaffolds bearing chains with different lengths (a = methoxy, b = 2-ethylhexan-1-oxy, c = 2-decyltetradecan-1-oxy) that are connected at either the para- or meta-position(s) of the phenyl bridging ring. The compounds feature either a linear (n = 1, para-substituted, series 8), two-armed (n = 1, meta-substituted series 9) or four-armed (n = 2, meta-substituted series 10) molecular architecture. Steady-state and time-resolved photophysical investigation is employed to characterize the optical properties of the compounds in both diluted CH2Cl2 and CH2Cl2:trifluoroacetic acid (TFA) 95:5 solutions, as well as in thin-film in poly(methyl methacrylate) (PMMA) matrix at 20 wt% doping. All compounds display electronic transitions with mainly π-π* nature at both solution and solid state. However, while both peripheral pyridyl-phenyl moieties and the π-TzTz-π core participate in the absorption transitions, the emission involves mostly the π-TzTz-π core. A clear effect of the positional isomerism on the photophysical properties is observed, with the protonation of the peripheral pyridines offering a further modulation. Thus, these results provide some useful hints on the molecular design of TzTz-based compounds as promising photoactive materials.

Structure and Conformation of Novel BODIPY Ugi Adducts.

Two novel BODIPY‐Ugi (boron dipyrromethene) adducts exhibit peculiar room temperature (T=20 °C) H‐1 NMR spectra in that several protons located at the aromatic aniline‐type ring are lost in the baseline. This observation revealed the existence of a dynamic conformational process where rotation around the C−N bond is hindered. Variable‐temperature H‐1 and C‐13 NMR spectroscopic analysis confirmed this conclusion; that is, low‐temperature spectra show distinct signals for all four aromatic protons below coalescence, whereas average signals are recorded above coalescence (T=+120 °C). Particularly interesting was the rather large difference in chemical shifts for the ortho protons below coalescence, Δδ=1.45 ppm, which was explained based on DFT computational analysis. Indeed, the calculated lowest‐energy gas‐phase conformation of the BODIPY Ugi adducts locates one half of the aniline‐type ring in the shielding anisotropic cone of the bridge phenyl ring in the BODIPY segment. This is in contrast to the solid‐state conformation established by X‐ray diffraction analysis that shows a nearly parallel arrangement of the aromatic rings, probably induced by crystal packing forces.

Synthesis and properties of AIE-active Triazaborolopyridiniums toward fluorescent nanoparticles for cellular imaging and their biodistribution in vivo and ex vivo

Three new aggregation-induced emission (AIE) molecules have been prepared by incorporation of the tetraphenylethylene (TPE) unit to the triazaborolopyridinium (TBP). The compounds exhibit broad absorption from 470 to 510 nm and emission from 530 to 600 nm in various solvents. The TPE-linked TBP, TT-1, and the compound with a phenylene bridge, TT-2, demonstrated high fluorescence quantum yields and solvent-sensitive behaviors due to twisted intramolecular charge transfer (TICT). In contrast, the derivative with a thiophene bridge, TT-3, showed less solvent dependence and low fluorescence quantum yield. The presence of a thiophene moiety led to redshift in the absorption and emission spectra due to a lower energy gap, confirmed by cyclic voltammetry (CV) and density functional theory (DFT) calculations. All derivatives displayed AIE in THF-water mixtures at water contents higher than 80% v/v. TT-1 was encapsulated within phospholipid-connected polyethylene glycol (DSPE-PEG) by nanoprecipitation, yielding fluorescent nanoparticles with the average sizes of 80.7–83.7 nm. In cell imaging experiments, the resulting TT-1@DSPE-PEG nanoparticles (NPs) showed no toxicity to H1299 lung carcinoma cells at concentrations up to 50 μM and were successfully internalized by the cells after 2 h incubation. Finally, the biodistribution of TT-1@DSPE-PEG NPs was studied in a bladder cancer murine model. In vivo and ex vivo images indicated that the NPs were highly localized in the stomach of the mouse after 2 h post-injection and showed a small uptake by the tumor after 4 h post-injection.

Thermodynamic Properties of a Hyperbranched Pyridylphenylene Polymer with a Phenylene Bridging Group

Thermodynamic Properties of a Hyperbranched Pyridylphenylene Polymer with a Phenylene Bridging Group

Controlling the Enantioselectivity in an Adaptable Ligand by Biomimetic Intramolecular Interlocking.

For the preparation of chiral drugs, both stereochemically stable and flexible catalysts in combination with chiral auxiliaries can be used. Here, chiral induction plays an important role in generating an enantiomerically pure catalyst. We demonstrate a successful approach to the spontaneous deracemization of tropos ligands for asymmetric catalysis. Three different constitutional isomers of a bisphosphinite ligand decorated with l-valine moieties (interaction units) linked to the flexible biphenyl system by a phenylene bridge for inducing a chiral switch were prepared. The substitution pattern's influence on the attached intermolecular recognition sites was systematically investigated. We can show that biomimetic intramolecular hydrogen bonding leads to a pronounced diastereoselective enrichment of one of the ligand stereoisomers. As a result, in the asymmetric Rh-catalyzed hydrogenation of prochiral olefins using these ligands, enantiomeric ratios of up to 95.8:4.2 (S) were obtained. Of particular note is the inversion of enantioselectivity relative to the previously reported BIBIPHOS-Rh catalyst due to the altered orientation of the biphenyl moiety from (Rax) to (Sax). The enantioselectivities achieved by appropriate intramolecular interlocking are remarkable for a tropos ligand/catalyst. The strategy presented here represents a powerful approach for the spontaneous alignment of tropos ligands, yielding high enantioselectivities in asymmetric catalysis.

Development and validation of stability indicating method for simultaneous estimation of Tezacaftor, Ivacaftor and Elexacaftor in tablet dosage form

This study aimed to optimize and validate methods for the analysis of Tezacaftor, Ivacaftor, and Elexacaftor. Method is optimized with X- Bridge phenyl (150x 4.6mm, 3.5µ) column at 210nm wavelength using Acetonitrile and 0.1% Formic acid 80:20 at 1 mL/min in isocratic mode. The injection volume is 10µL at 25 C. According to ICH guidelines, the approach was validated for system suitability, specificity, linearity, robustness, precision, and accuracy. The limit of detection (µg/mL) for Tezacaftor, Ivacaftor, and Elexacaftor is found to be 0.060, 0.098, and 0.13 respectively. The limit of quantification (µg/mL) is found to be 0.21, 0.33, and 0.37 respectively. Forced degradation studies using various conditions like acid, base, peroxide, thermal, U.V, reduction, control, and hydrolysis were carried out and in all cases and the peak purity passes. Thus the method is found as stability indicating as per ICH guidelines. Keywords: Tezacaftor, Ivacaftor, and Elexacaftor, RP-HPLC, Validation, Forced degradation.

Tetra-Carbazole based electroactive donor-acceptor dyes: Effect of the phenyl bridging unit on the electrochromic performance

In this study, a new Donor-Acceptor-Donor (D-A-D) electroactive molecules (HCQM1 and HCQM2) containing 9H-carbazole and 9-phenyl-9H-carbazole as donor along with quinoxaline (HQ) as acceptor were synthesized and then coated on Indium Tin Oxide/Glass (ITO/Glass) surface by the electrochemical oxidation process. The HOMO-LUMO band gap values obtained by electrochemical oxidation and reduction onsets were calculated as 2.64 and 2.68 eV, respectively. On the other hand, UV–Vis absorption measurements showed that the charge transfer band of HCQM1 was detected at 500 nm with 50 nm red shift upon compared with the HCQM2. According to AFM results, it is seen that the roughness of the poly(HCQM2) film is higher than the poly(HCQM1) film. Finally, the polymer film of HCQM2 showed multi-electrochromic color change (yellow, green, and dark blue) upon the oxidation process. When the electrochromic performance of the HCQM1 and HCQM2 polymer films was compared, it was discovered that the HCQM2 with phenylene spacer unit has better stability and a higher percentage transmittance change (ΔT%) between neutral and oxidized states.

Substituent effect on TADF properties of 2-modified 4,6-bis(3,6-di-tert-butyl-9-carbazolyl)-5-methylpyrimidines.

The interest in organic materials exhibiting thermally activated delayed fluorescence (TADF) significantly increased in recent years owing to their potential application as emitters in highly efficient organic light emitting diodes (OLEDs). Simple modification of the molecular structure of TADF compounds through the selection of different electron-donating or accepting fragments opens great possibilities to tune the emission properties and rates. Here we present the synthesis of a series of novel pyrimidine–carbazole emitters and their photophysical characterization in view of effects of substituents in the pyrimidine ring on their TADF properties. We demonstrate that electron-withdrawing substituents directly connected to the pyrimidine unit have greater impact on the lowering of the energy gap between singlet and triplet states (ΔEST) for efficient TADF as compared to those attached through a phenylene bridge. A modification of the pyrimidine unit with CN, SCH3, and SO2CH3 functional groups at position 2 is shown to enhance the emission yield up to 0.5 with pronounced TADF activity.

Turn-on fluorescence probe for BSA detection and selective cell imaging

In this paper, a cationic amphiphile (denoted by DPP-10) with diketopyrrolopyrrole decorated with methoxylated tetraphenylethylene via a phenyl bridge was designed, synthesized, and applied as a turn-on fluorescence probe for bovine serum albumin (BSA) detection and selective cell imaging. DPP-10 showed very weak fluorescence emission when dispersed in the solution, while its emission was drastically enhanced upon the addition of BSA, which should be attributed to the electrostatic interaction-driven assembly between DPP-10 and BSA. The limit of detection was as low as 0.08 μmol/L, which is lower than that reported for most probes. The fluorescence probe shows good selectivity for BSA among the tested proteins, high photostability, and immunity to the disturbance of ions. DPP-10 with excellent cytocompatibility was applied to HeLa cell imaging, where only the BSA-rich cells showed a strong signal-to-background contrast.

Protein encapsulation in mesoporous silica: Influence of the mesostructured and pore wall properties

The goal of this work is to study the influence of the structured mesoporous silica (SMS), used as scaffolds for tissue engineering, on the encapsulation and on the release of a model bone morphogenetic proteins (BMP), i.e. Soybean Trypsin Inhibitor (STI). First, SBA-15 silica samples were synthesized using tetraethyl orthosilicate (TEOS) as silica precursor in the presence of P123 as the surfactant in an acidic medium. Three homemade high-pressure stainless steel reactors (with smaller Teflon reactors inside), each equipped with a temperature probe, were used for the syntheses. In addition, a swelling agent was added to increase the pore size. Indeed, the common pore size for those mesostructured materials lies between 6 nm and 8 nm, while the STI has an average radius of 4 nm. The reagent addition sequence was also investigated, by playing on the time of addition of the swelling agent. It was observed that when the swelling agent was added with TEOS, an ordered mesoporous silica was produced. On the contrary, if the swelling agent was added during the surfactant dissolution step, it resulted in an unstructured yet still mesoporous silica. Because of the high affinity of STI for hydrophobic surfaces, SMS were also produced using silica precursors containing phenylene bridging groups (1,4-bis(triethoxysilyl)benzene, BTEB). The BTEB samples exhibited two 2D-hexagonal structures with different wall thicknesses. Synthesized materials were further characterized by infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), nitrogen sorption at 77 K, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). The influence of both the silica composition and structure on STI encapsulation/release was studied. For samples synthesized with TEOS, the unstructured sample showed a higher protein loading and a higher protein release, which could be explained by a difference in the pore interconnectivity within the sample. In fact, a fast release of STI was observed during the first 24 h. Afterwards, the STI release slowed down and seemed to reach a plateau. On the opposite, the structured sample showed a steady release over time. Finally, the sample synthesized with BTEB did not show a significant release over the same period of time. This led us to the conclusion that the hydrophobicity of the silica surface plays a major role on the protein encapsulation and its release rate.

Peri-N-amine-perylenes, with and without phenyl bridge: Photophysical studies and their OLED applications

Donor-bridge-acceptor framework has been studied widely for their detailed photophysical properties with the aim of efficient long range charge transfer. Carbazole attached with electron acceptors has been used for charge transfer properties, thermally activated delayed fluorescence, exciton dynamics etc. In this study, we synthesized donor–acceptor dyads of seconday amine (carbazole and diphenyl amine) attached to perylene through nitrogen, with phenyl (P-Ph-N-CBZ and P-Ph-N-BP) and without phenyl (P-N-CBZ and P-N-BP). Further their detailed photophysical and electroluminescent properties are discussed. P-N-BP is known and is used as standard in this work. DFT studies show nearly orthogonal geometry of P-N-CBZ with the dihedral angle of ∼ 71° between the planes of perylene and carbazole. For P-Ph-N-BP and P-Ph-N-CBZ, the perylene and amines are adopting almost co-planar geometries. Emission spectra of P-Ph-N-CBZ and P-N-CBZ in dichloromethane are structural with clear vibronic features while for P-Ph-N-BP and P-N-BP, the emission is structureless and broad indicating prominent electronic coupling between molecular orbitals of donor and acceptor in the latter case. Fluorescence quantum yields of phenyl-linked dyads are found to be higher than directly linked perylene-amine derivatives. High quantum yield (0.79) in non-polar hexane and polar DMSO (0.66) is observed for P-Ph-N-CBZ. It is interesting to note that the fluorescence lifetimes of these dyads are increasing while fluorescence quantum yields are decreasing with increasing polar solvents, suggesting that the emission has a significant contribution from the 1CT state. Dipole moments estimated from DFT studies and photophysical methods are higher for phenyl-linked dyads than those directly attached which is also consistent with their solvatochromism properties. Weaker electronic coupling in phenyl-linked dyads resulted due to the long distance between donor and acceptor in phenyl-linked dyads. Furthermore application in OLEDs was shown for P-Ph-N-CBZ and P-Ph-N-BP. OLEDs of P-Ph-N-BP showed a peak emission at 568 nm resulting in an amber device. A high luminance of 4.3 × 103 Cd/m2 at a current density of 100 mA/cm2 and a maximum EQE of 4.2% with a low turn on volatage of ∼ 4 V was obtained for these devices. Thus, our results show that weaker charge transfer takes place in perylene based donor–acceptor dyads resulting in bright OLED devices.

Kinetic Stabilization of Blue-Emissive Anthracenes: Phenylene Bridging Works Best.

In attempts at kinetically stabilizing blue‐emissive anthracenes, a series of 9,10‐diaryl substituted derivatives were tested for their photochemical and photooxidative persistence. A major breakthrough in light fastness comes from a new bis‐meta‐terphenylyl substituted anthracene which is much superior to industrially relevant 9,10‐biarylated anthracenes. The key issue is the steric shielding of the anthracene core. Further, intramolecular ring closure via Yamamoto coupling furnished a doubly bridged anthracene as a “self‐encapsulated” sky‐blue emitter which is most resistant to photodegradation. The improved stabilization was corroborated by time‐resolved irradiation experiments and rationalized by X‐ray crystallography.

Endowing imidazole derivatives with thermally activated delayed fluorescence and aggregation‐induced emission properties for highly efficient non‐doped organic light‐emitting diodes

AbstractThe development and enrichment of high‐performance organic fluorophores that simultaneously possess thermally activated delayed fluorescence (TADF) and aggregation‐induced emission (AIE) properties is going pursued but remains a great challenge due to severe exciton quenching. Herein, a systematical investigation on imidazole moiety has successfully given rise to a series of highly efficient imidazole‐based TADF‐AIE luminogens for the first time. The attachment of two cyano functionalities on imidazole moiety can significantly increase the electron‐withdrawing ability, so as to realize TADF emissions with small singlet‐triplet energy gaps (ΔEST) values. Meanwhile, the installation of a steric hindrance group at N1 position of imidazole moiety can twist the geometry between imidazole and phenyl bridge, thus transforming imidazole derivative from an aggregation‐caused quenching emitter into an AIE luminogen. Consequently, the non‐doped organic light‐emitting diodes (OLEDs) utilizing these TADF‐AIE luminogens as emitters exhibit outstanding sky‐blue and green emissions, with external quantum efficiency (EQE) as high as 20.0% and low efficiency roll‐off (EQE at 1000 cd m−2, 16.1%). These values represent the state‐of‐the‐art performance for all imidazole‐based OLED devices, which illustrates the significant potential of imidazole derivatives in assembling high‐performance OLEDs.

Amino−Organolithium Compounds and their Aggregation for the Synthesis of Amino−Organoaluminium Compounds

AbstractHere, we present a thorough structural study of small, easily accessible amino−organolithium compounds with bridging phenyl and naphthyl moieties. Their crystal structures most likely represent their aggregation as tetramers and dimers in both hydrocarbon and ethereal solvents. These amino−organolithium compounds were further used to generate their corresponding aluminium compounds as a model system. Their crystal structures are reported too. All structures are discussed with a focus on the different steric demands and bridging moieties. Additionally, the crystal structures of neophyllithium and decomposition products of some of the compounds mentioned above are reported. This study provides additional data for the future design and synthesis of amine stabilised organolithium and ‐aluminium compounds.

NSSN-Type Group 4 Metal Complexes in the Ring-Opening Polymerization of l-Lactide.

A new class of zirconium and hafnium complexes coordinated by linear dianonic tetradentate NSSN ligands is reported. The ligands feature two amide functions coupled with two thioether groups linked by a central flexible ethane bridge and two lateral rigid phenylene bridges and differ for the substituents on the aniline nitrogen atoms, i.e., isopropyl, cyclohexyl, or mesityl substituents: NSSN-iPr, NSSN-Cy, or NSSN-Mes. They were prepared by reacting 2-aminothiophenol with dibromoethane to afford the NSSN ligands without substituents on the aniline nitrogen atoms, which were subsequently alkylated through a reductive amination of acetone or cyclohexanone or palladium-catalyzed cross-coupling reaction with mesityl bromide. The corresponding zirconium and hafnium complexes 1-5 were obtained through a transamination reaction between the neutral ligands and Zr(NMe2)4 or Hf(NMe2)4 [(NSSN-iPr)Zr(NMe2)2 (1), (NSSN-Cy)Zr(NMe2)2 (2), (NSSN-Mes)Zr(NMe2)2 (3), (NSSN-iPr)Hf(NMe2)2 (4), and (NSSN-Cy)Hf(NMe2)2 (5)]. They were characterized in solution by NMR spectroscopy and in solid state by X-ray diffraction analysis (except for 3). All complexes present an octahedral coordination geometry with a fac-fac ligand wrapping and a cis relationship between the other two monodentate ligands. The catalytic performances of 1-5 in the ring-opening polymerization of cyclic esters were investigated. Complex 1 was the most active: its polymerization activity was superior to those generally displayed by zirconium complexes featuring OSSO ligands and compared well with those of the most active group 4 complexes operating in a toluene solution.

A Dicopper Nitrenoid by Oxidation of a CuICuI Core: Synthesis, Electronic Structure, and Reactivity.

A dicopper nitrenoid complex was prepared by formal oxidative addition of the nitrenoid fragment to a dicopper(I) center by reaction with the iminoiodinane PhINTs (Ts = tosylate). This nitrenoid complex, (DPFN)Cu2(μ-NTs)[NTf2]2 (DPFN = 2,7-bis(fluorodi(2-pyridyl)methyl)-1,8-naphthyridine), is a powerful H atom abstractor that reacts with a range of strong C-H bonds to form a mixed-valence Cu(I)/Cu(II) μ-NHTs amido complex in the first example of a clean H atom transfer to a dicopper nitrenoid core. In line with this reactivity, DFT calculations reveal that the nitrenoid is best described as an iminyl (NR radical anion) complex. The nitrenoid was trapped by the addition of water to form a mixed-donor hydroxo/amido dicopper(II) complex, which was independently obtained by reaction of a Cu2(μ-OH)2 complex with an amine through a protonolysis pathway. This mixed-donor complex is an analogue for the proposed intermediate in copper-catalyzed Chan-Evans-Lam coupling, which proceeds via C-X (X = N or O) bond formation. Treatment of the dicopper(II) mixed donor complex with MgPh2(THF)2 resulted in generation of a mixture that includes both phenol and a previously reported dicopper(I) bridging phenyl complex, illustrating that both reduction of dicopper(II) to dicopper(I) and concomitant C-X bond formation are feasible.