High Quantum Yields from Perfluorinated Binolate Erbium Complexes and Their Circularly Polarized Luminescence.

High quantum yield and circularly polarized luminescence (CPL) brightness values are reported from Shibasaki-type erbium complexes supported by a perfluorinated Binol ligand (F12Binol). The total fluorination of the ligand circumvents nonradiative quenching from Csp2-H vibrations and leads to quantum yields of up to 11% and CPL brightness values of up to 317 M-1 cm-1 (a 19- and 6-fold increase, respectively, compared to (Binol)3ErNa3). These values are the highest values for any molecular erbium complex to date, making them comparable to Yb emitters. A series of fluorinated Shibasaki-type complexes are synthesized by varying the alkali metal (K, Na, Li) in the secondary coordination sphere, leading to unexpected structural differences. NMR (19F, 7Li) and chiroptical spectroscopy analyses provide insights into their structural geometry. With much improved quantum yields and CPL brightness values, we provide synthetic design principles toward other practical candidates for use in quantum communication technologies.

Augmentation of NIR Circularly Polarized Luminescence Activity in Shibasaki-Type Lanthanide Complexes Supported by the Spirane Sphenol.

We report two new circularly polarized luminescence (CPL)-active lanthanide complexes emissive in the near-infrared (NIR) region; using sphenol as a supporting ligand, we provide the first reported example of an NIR-emissive lanthanide complex supported by a chiral spirane. Inclusion of a quaternary carbon to impart axial chirality results in dramatic augmentation of the CPL strength of the resultant sphenolate complexes (glum ≤ 0.77 for [(sphenol)3ErNa3(thf)6]) compared to that of their contemporary biaryl-based axially chiral analogues (glum ≤ 0.47 for [(binol)3ErNa3(thf)6]). Despite similar structural parameters, the rigid spiro carbon of sphenol enables the strongest dissymmetry factors observed to date from Shibasaki-type complexes for both Yb and Er. We also demonstrate the sensitivity of the reported chiroptical measurements to small variations in instrumental parameters, such as bandpass, and suggest a standardized method or at least that additional detail should be included in future reports to allow for direct comparisons between newly published CPL emitters.

Electronic Structure of Metallophlorins: Lessons from Iridium and Gold Phlorin Derivatives.

Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of 5,5-dimethyl-10,15,20-tris(pentafluorophenyl)phlorin. Theory and experiments concur that the phlorin derivatives exhibit substantially smaller HOMO-LUMO gaps, as reflected in a variety of observable properties. Thus, the experimentally studied Ir and Au complexes absorb strongly in the near-infrared (NIR), with absorption maxima at 806 and 770 nm, respectively. The two complexes are also weakly phosphorescent with emission maxima at 950 and 967 nm, respectively. They were also found to photosensitize singlet oxygen formation, with quantum yields of 40 and 28%, respectively. The near-infrared (NIR) absorption and emission are consonants with smaller electrochemical HOMO-LUMO gaps of ∼1.6 V, compared to values of ∼2.1 V, for electronically innocent porphyrins and corroles. Interestingly, both the first oxidation and reduction potentials of the Ir complex are some 600 mV shifted to more negative potentials relative to those of the Au complex, indicating an exceptionally electron-rich macrocycle in the case of the Ir complex.

Bis-oxazoline derivatives as ancillary ligands for bis-cyclometalated iridium complexes.

Organometallic iridium complexes with two cyclometalated ligands (CN) and one bis-oxazoline derived ancillary ligand (L^X), i.e. (CN)2Ir(L^X), are reported. The CN ligands are 1-phenylpyrazoline (ppz), 2-(4,6-difluorophenyl)pyridine (F2ppy), 2-phenylpyridine (ppy), 1-phenylisoquinoline (piq). The box ligand is (4S)-(+)-phenyl-α-[(4S)-phenyloxazolidin-2-ylidene]-2-oxazoline-2-acetonitrile. The emission of these complexes span across the visible and into the near-ultraviolet region of the electromagnetic spectrum with moderate to high photoluminescence quantum yields (ΦPL = 0.45-1.0). These complexes were found to emit from a metal-ligand to ligand charge transfer (ML'LCT) state and have lifetimes (1.3-2.1 µs), radiative rates (105 s-1), and nonradiative rates (104-105 s-1) comparable to state-of-the-art iridium emitters. The (ppy)2Ir(BOX-CN) complexes were resolved into the Δ- and Λ- diastereomers using differences in their solubility and additionally characterized by x-ray crystallography, stability, and chiroptic studies. The high ΦPL of these isomers results in the best to date brightness for circularly polarized luminescence (CPL) from iridium complexes (7.0 M-1 cm-1), with dissymmetry factors of -0.57 × 10-3 and +1.9 × 10-3 for 3Δ and 3Λ, respectively. The significant difference in CPL magnitude between 3Δ and 3Λ likely arises from interligand interactions (edge-to-face arrangement versus strong π-π interaction) for the pendant phenyl ring of the BOX-CN ligand which differ for the two isomers.

Improved Energy Transfer in the Sensitization of Americium Enables Observation of Circularly Polarized Luminescence.

The first example of circularly polarized luminescence (CPL) from a molecular americium (Am) complex is reported. Coordination of Am(III) by a combination of thenoyltrifluoroacetonate and chiral diphosphine oxide ligands yielded a complex with strong sensitized metal-centered luminescence. The energy transfer process for sensitization appears to occur via a unique resonant pathway, which results in the removal of the overlap between ligand phosphorescence and sensitized Am luminescence that has always been observed. Owing to this feature, and despite the limited amount of material that could be used due to the radioactivity of 241Am, CPL could be measured. The collected luminescence and CPL spectra provide insight into the crystal field splitting of the 5D1 → 7F1 transition. These results pave the way for future studies of Am(III) luminescence to investigate electronic structure effects in this and other 5f elements.

Vanol-Supported Lanthanide Complexes for Strong Circularly Polarized Luminescence at 1550†nm.

Strong circularly polarized luminescence (CPL) at 1550 nm is reported for lanthanide complexes supported by Vanol; these are the first examples of coordination of Vanol to lanthanides. A change in the ligand design from a 1,1'-bi-2-naphthol (in Binol) to a 2,2'-bi-1-naphthol (in Vanol) results in significantly improved dissymmetry factors for (Vanol)3 ErNa3 (|glum |=0.64) at 1550 nm. This is among the highest reported dissymmetry factors to date in the telecom C-band region, and among the highest for any lanthanide complexes. Comparative solid-state structural analysis of (Vanol)3 ErNa3 and (Binol)3 ErNa3 suggests that a less distorted geometry around the metal center is in part responsible for the high chiroptical metrics of (Vanol)3 ErNa3 . This phenomenon was further evidenced in the analogous ytterbium complex (Vanol)3 YbNa3 that also exhibit a significantly improved dissymmetry factor (|glum |=0.21). This confirms and generalizes the same observation that was made in other visibly emitting, six-coordinate lanthanide complexes. Due to their strong CPL at 1550 nm, the reported complexes are potential candidates for applications in quantum communication technologies. More importantly, our structure-CPL activity relationship study provides guidance towards the generation of even better near-infrared CPL emitters.

Transition-Metal Isocorroles as Singlet Oxygen Sensitizers.

Building on a highly efficient synthesis of pyrrole-appended isocorroles, we have worked out conditions for manganese, palladium, and platinum insertion into free-base 5/10-(2-pyrrolyl)-5,10,15-tris(4-methylphenyl)isocorrole, H2[5/10-(2-py)TpMePiC]. Platinum insertion proved exceedingly challenging but was finally accomplished with cis-Pt(PhCN)2Cl2. All the complexes proved weakly phosphorescent in the near-infrared under ambient conditions, with a maximum phosphorescence quantum yield of 0.1% observed for Pd[5-(2-py)TpMePiC]. The emission maximum was found to exhibit a strong metal ion dependence for the 5-regioisomeric complexes but not for the 10-regioisomers. Despite the low phosphorescence quantum yields, all the complexes were found to sensitize singlet oxygen formation with moderate to good efficiency, with singlet oxygen quantum yields ranging over 21-52%. With significant absorption in the near-infrared and good singlet oxygen-sensitizing ability, metalloisocorroles deserve examination as photosensitizers in the photodynamic therapy of cancer and other diseases.

Circularly Polarized Luminescence from Uranyl Improves Resolution of Electronic Transitions.

The first reported example of circularly polarized luminescence from a chiral, molecular uranyl (UO22+) complex in solution is presented. This uranyl chiroptical activity is enabled by complexation with ibuprofen, an enantiopure chiral carboxylate ligand. Salt metathesis between [UO2Cl2(thf)2]2 and the sodium ibuprofenate salts results in the formation of the anionic tris complexes; these complexes are found to be luminescent in solution, both under visible excitation, directly targeting the metal, and through sensitization by UV absorption and energy transfer from the ligand. Each enantiomer displays both circular dichroism and circularly polarized luminescence (CPL) with |gabs| ≤ 8.1 × 10-2 and |glum| ≤ 8.0 × 10-3 under UV excitation, comparable to chiral transition metal complexes or purely organic emitters. The strength of the CPL emission is found to be comparable following excitation of either the ligand or metal directly. Further, use of CPL allows for resolution of subcomponents of the emission spectrum not previously possible at room temperature using standard fluorescence techniques. Observation of CPL following direct uranyl excitation presents a new tool for probing speciation of uranyl complexes when chiral ligands are used, without the need for synthetic modification to incorporate a suitable chromophore, and could enable the design of improved ligands for uranyl extraction from wastewater.

Strong Circularly Polarized Luminescence at 1550 nm from Enantiopure Molecular Erbium Complexes.

Circularly polarized luminescence (CPL) in two subregions of the near-infrared (NIR) has been achieved. By leveraging the rigidity and diminishing detrimental vibrations of the heterobimetallic binolate complexes of erbium [(Binol)3ErNa3], species exhibiting an exceptionally high dissymmetry factor (|glum |) of 0.47 at 1550 nm were obtained. These erbium complexes are the first reported examples of CPL observed beyond 1200 nm. Analogous complexes of ytterbium and neodymium also exhibited strong CPL (|glum| = 0.17, 0.05, respectively) in a higher energy NIR window (800-1200 nm). All complexes exhibit high quantum yields (Er: 0.58%, Yb: 17%, Nd: 9.3%) and high BCPL values (Er: 57 M-1 cm-1, Yb: 379 M-1 cm-1, Nd: 29 M-1 cm-1). Because of their strong CPL emission in the telecom band (1550 nm), biologically relevant NIR emission window (800-1100 nm), and synthetic versatility, the complexes reported here could permit further promising developments in quantum communication technologies and biologically relevant sensors.

Spinolate Lanthanide Complexes for High Circularly Polarized Luminescence Metrics in the Visible and Near-Infrared.

Analogues of Shibasaki's complexes supported by enantiopure Spinol are synthesized and characterized. The tris(Spinol) LnIII complexes are generated either by ligand deprotonation followed by complexation with lanthanide triflate salts or by in situ deprotonation by Ln(N(SiMe3)2)3 salts in the presence of additional base. The resulting complexes are found to be luminescent and chiroptically active for both circular dichroism and circularly polarized luminescence (CPL), notably producing strong CPL with dissymmetry factors (glum) of up to 0.50, 0.53, and 0.53 for Sm, Tb, and Dy, respectively. The Sm complex is found to be CPL-active in the near-infrared (NIR) region at 980 nm, representing the first report of NIR CPL from Sm. Additionally, the Tb complex, due to efficient sensitization (Φ = 0.846 in tetrahydrofuran) coupled with strong dissymmetry factors, achieves a CPL brightness (BCPL) of 3760 M-1 cm-1, the highest reported for any CPL-active compound to date. These are rare examples of compounds that show simultaneous improvement of both CPL metrics (glum and BCPL). Solid-state structural analysis of the Spinolate complexes and comparisons to other CPL-active analogues of Shibasaki's complexes also suggest that nondistorted geometries should generate even stronger metrics.

Circularly Polarized Luminescence from Enantiopure C2-Symmetrical Tetrakis(2-pyridylmethyl)-1,2-diaminocyclohexane Lanthanide Complexes.

We report the synthesis and characterization of C2-symmetrical lanthanide complexes supported by enantiopure hexadentate ligands derived from 1,2-diaminocyclohexane. Coordination of (R,R)- or (S,S)-N,N,N',N'-tetrakis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane (tpdac) to samarium, europium, terbium, and dysprosium generates the corresponding C2-symmetrical (tpdac)Ln(OTf)3 complexes in high yields. The tpdac ligands are competent sensitizers for lanthanide luminescence, yielding modest emissions (Φ of ≤28%). Additionally, the complexes exhibit strong circularly polarized luminescence (|glum| values of up to 0.13, 0.09, 0.22, and 0.15 for Sm, Eu, Tb, and Dy, respectively) in solution. We also observed that some transitions typically associated with small dissymmetry factors exhibit unusually high |glum| values and, therefore, should not be overlooked in future studies.

Synthesis of Enantiopure Lanthanide Complexes Supported by Hexadentate N,N'-Bis(methylbipyridyl)bipyrrolidine and Their Circularly Polarized Luminescence.

We report the synthesis of lanthanide complexes supported by enantiopure N,N'-bis(methylbipyridyl)bipyrrolidine and subsequent characterization through luminescence studies. Complexes of this ligand with the visibly emissive lanthanides Sm, Eu, Tb, and Dy are luminescent (ϕf of ≤0.32) and demonstrate strong preferential emission of circularly polarized light in all four cases (|glum| of ≤0.26). Notably, all four possess at least one transition with a |glum| of >0.2, and the strongest preferential emission is measured from the complexes of Sm and Dy.

Yellow Circularly Polarized Luminescence from C1 -Symmetrical Copper(I) Complexes.

The synthesis of chiral C1 -symmetrical copper(I) complexes supported by chiral carbene ligands is described. These complexes are yellow emitters with modest quantum yields. Circularly polarized luminescence (CPL) spectra show a polarized emission band with dissymmetry factors |glum |=1.2×10-3 . These complexes are the first reported examples of molecular copper(I) complexes exhibiting circularly polarized luminescence. In contrast with most CPL-emitting molecules, which possess either helical or axial chirality, the results presented show that simple chiral architectures are suitable for CPL emission and unlock new synthetic possibilities.

A Polymer Solution To Prevent Nanoclustering and Improve the Selectivity of Metal Nanoparticles for Electrocatalytic CO2 Reduction.

The stability of metal nanocatalysts for electrocatalytic CO2 reduction is of key importance for practical application. We report the use of two polymeric N-heterocyclic carbenes (NHC) (polydentate and monodentate) to stabilize metal nanocatalysts (Au and Pd) for efficient CO2 electroreduction. Compared with other conventional ligands including thiols and amines, metal-carbene bonds that are stable under reductive potentials prevent the nanoclustering of nanoparticles. Au nanocatalysts modified by polymeric NHC ligands show an activity retention of 86 % after CO2 reduction at -0.9 V for 11 h, while it is less than 10 % for unmodified Au. We demonstrate that the hydrophobicity of polymer ligands and the enriched surface electron density of metal NPs through σ-donation of NHCs substantially improve the selectivity for CO2 reduction over proton.

Solvent-Dependent Sensitization of Ytterbium and Neodymium via an Intramolecular Excimer.

We report the synthesis of a di(1-pyrenyl)phosphoryl acetophenone ligand containing two pyrenyl moieties linked by a single phosphorus atom. The ligand exhibits solvent-dependent emission: in nonpolar solvents, typical monomeric pyrene emission is observed, whereas in polar solvents, an additional broad and structureless emission appears. The emission in polar solvents is concentration independent and is attributed to the emission of an intramolecular excimer. The coordination of the di(1-pyrenyl)phosphoryl acetophenone ligand as well as the corresponding deprotonated anionic di(1-pyrenyl)phosphoryl acetophenonate ligand was studied with the near-infrared emitting lanthanides, neodymium and ytterbium. Solvent-dependent sensitization of both lanthanides was observed and correlates with the presence of the excimer emission. Sensitization of ytterbium is more efficient than neodymium, and the overall quantum yields were found to be 12.8 and 1.9% for ytterbium and neodymium, respectively.

Evaluating molecular cobalt complexes for the conversion of N2 to NH3.

Well-defined molecular catalysts for the reduction of N2 to NH3 with protons and electrons remain very rare despite decades of interest and are currently limited to systems featuring molybdenum or iron. This report details the synthesis of a molecular cobalt complex that generates superstoichiometric yields of NH3 (>200% NH3 per Co-N2 precursor) via the direct reduction of N2 with protons and electrons. While the NH3 yields reported herein are modest by comparison to those of previously described iron and molybdenum systems, they intimate that other metals are likely to be viable as molecular N2 reduction catalysts. Additionally, a comparison of the featured tris(phosphine)borane Co-N2 complex with structurally related Co-N2 and Fe-N2 species shows how remarkably sensitive the N2 reduction performance of potential precatalysts is. These studies enable consideration of the structural and electronic effects that are likely relevant to N2 conversion activity, including the π basicity, charge state, and geometric flexibility.

Low-temperature N2 binding to two-coordinate L2Fe(0) enables reductive trapping of L2FeN2(-) and NH3 generation.

The two-coordinate [(CAAC)2Fe] complex [CAAC = cyclic (alkyl)(amino)carbene] binds dinitrogen at low temperature (T<-80 °C). The resulting putative three-coordinate N2 complex, [(CAAC)2Fe(N2)], was trapped by one-electron reduction to its corresponding anion [(CAAC)2FeN2](-) at low temperature. This complex was structurally characterized and features an activated dinitrogen unit which can be silylated at the ß-nitrogen atom. The redox-linked complexes [(CAAC)2Fe(I)][BAr(F)4], [(CAAC)2Fe(0)], and [(CAAC)2Fe(-I)N2](-) were all found to be active for the reduction of dinitrogen to ammonia upon treatment with KC8 and HBAr(F)4⋅2 Et2O at -95 °C [up to (3.4±1.0) equivalents of ammonia per Fe center]. The N2 reduction activity is highly temperature dependent, with significant N2 reduction to NH3 only occurring below -78 °C. This reactivity profile tracks with the low temperatures needed for N2 binding and an otherwise unavailable electron-transfer step to generate reactive [(CAAC)2FeN2](-) .

Two-coordinate Fe° and Co° complexes supported by cyclic (alkyl)(amino)carbenes.

The CAAC [CAAC=cyclic (alkyl)(amino)carbene] family of carbene ligands have shown promise in stabilizing unusually low-coordination number transition-metal complexes in low formal oxidation states. Here we extend this narrative by demonstrating their utility in affording access to the first examples of two-coordinate formal Fe(0) and Co(0) [(CAAC)2M] complexes, prepared by reduction of their corresponding two-coordinate cationic Fe(I) and Co(I) precursors. The stability of these species arises from the strong σ-donating and π-accepting properties of the supporting CAAC ligands, in addition to steric protection.

Magnetic Assembly of Eu-Doped NaYF4 Nanorods for Field-Responsive Linearly and Circularly Polarized Luminescence.

Colloidal assembly has emerged as an effective avenue for achieving polarized light emission. Here, we showcase the efficacy and versatility of the magnetic colloidal assembly in enabling both linearly and circularly polarized luminescence. Colloidal europium-doped NaYF4 nanorods with surface-bound Fe3O4 nanoparticles are magnetically assembled into linear or chiral superstructures using corresponding fields created in permanent magnets. In a uniform magnetic field generated by opposing poles, the assemblies exhibit photoluminescence with intensity tunable in response to the magnetic field direction, which is higher when the nanorods are perpendicular to light propagation than when they are parallel. The obtained superstructures display strong linearly polarized luminescence when the nanorods are aligned vertically, exhibiting a high degree of polarization up to 0.61. In a quadrupole chiral field generated by permanent magnets, the assemblies emit left-handed or right-handed polarized light depending on the position of the sample placement, attaining a g-factor of 0.04. Furthermore, the superstructures immobilized in a hydrogel film are found to retain their chirality, exhibiting opposite chiroptical responses depending on the sample orientation. The magnetic colloidal assembly approach facilitates the convenient and efficient generation of polarized light emissions from nonmagnetic luminescent materials, thus creating opportunities for tailoring light behavior in developing innovative optoelectronic devices.

ß- and α-Hydride abstraction in Gold(I) alkyl complexes.

Why not both? Both ß- and α-hydrogen atoms of gold alkyl complexes are hydridic enough to be abstracted, opening a new route to gold-alkene and gold-carbene complexes, respectively.