A [2.2]Isoindolinophanyl-Based Carbene (iPC) Ligand: Synthesis, Electronic and Photophysical Properties, and Application in Photocatalysis*.

Cyclic amino(alkyl) and cyclic amino(aryl) carbenes (cAACs/cAArCs) have been established as very useful ligands for catalytic and photonic applications of transition metal complexes. Herein, we describe the synthesis of a structurally related sterically demanding, electrophilic [2.2]isoindolinophanyl-based carbene (iPC) with a [2.2]paracyclophane moiety. The latter leads to more delocalized frontier orbitals and intense green fluorescence of (HiPC)OTf (2) from an intra-ligand charge transfer (1ILCT) state in the solid state. Base-promoted synthesis of the free carbene led to an unusual ring expansion and subsequent dimerization reaction, but the beneficial ligand properties can be exploited by trapping in situ at a metal center. The iPC ligand is a very potent π-chromophore, which participates in low energy metal-to-ligand (ML)CT transitions in [RhCl(CO)2(iPC)] (4) and IL-"through-space"-CT transitions in [Au(iPC)2]OTf (5). The steric demand of the iPC leads to high stability of 5 against air, moisture, or solvent attack, and ultralong-lived green phosphorescence with a lifetime of 185 µs is observed in solution. The beneficial photophysical and electronic properties of the iPC ligand, including a large accessible π surface area, were exploited by employing highly efficient energy transfer (EnT) photocatalysis in a [2+2] styrene cycloaddition reaction using 5, which outperformed other established photocatalysts in comparison.

Structural Control of Highly Efficient Thermally Activated Delayed Fluorescence in Carbene Zinc(II) Dithiolates.

Luminescent metal complexes based on earth abundant elements are a valuable target to substitute 4d/5d transition metal complexes as triplet emitters in advanced photonic applications. Whereas CuI complexes have been thoroughly investigated in the last two decades for this purpose, no structure-property-relationships for efficient luminescence involving triplet excited states from ZnII complexes are established. Herein, we report on the design of monomeric carbene zinc(II) dithiolates (CZT) featuring a donor-acceptor-motif that leads to highly efficient thermally activated delayed fluorescence (TADF) with for ZnII compounds unprecedented radiative rate constants kTADF =1.2×106  s-1 at 297 K. Our high-level DFT/MRCI calculations revealed that the relative orientation of the ligands involved in the ligand-to-ligand charge transfer (1/3 LLCT) states is paramount to control the TADF process. Specifically, a dihedral angle of 36-40° leads to very efficient reverse intersystem-crossing (rISC) on the order of 109  s-1 due to spin-orbit coupling (SOC) mediated by the sulfur atoms in combination with a small ΔES1-T1 of ca. 56 meV.

Synthesis, Structural Characterization, and Phosphorescence Properties of Trigonal Zn(II) Carbene Complexes.

The sterically demanding N-heterocyclic carbene ITr (N,N'-bis(triphenylmethyl)imidazolylidene) was employed for the preparation of novel trigonal zinc(II) complexes of the type [ZnX2(ITr)] [X = Cl (1), Br (2), and I (3)], for which the low coordination mode was confirmed in both solution and solid state. Because of the atypical coordination geometry, the reactivity of 1-3 was studied in detail using partial or exhaustive halide exchange and halide abstraction reactions to access [ZnLCl(ITr)] [L = carbazolate (4), 3,6-di-tert-butyl-carbazolate (5), phenoxazine (6), and phenothiazine (7)], [Zn(bdt)(ITr)] (bdt = benzene-1,2-dithiolate) (8), and cationic [Zn(µ2-X)(ITr)]2[B(C6F5)4]2 [X = Cl (9), Br (10), and I (11)], all of which were isolated and structurally characterized. Importantly, for all complexes 4-11, the trigonal coordination environment of the ZnII ion is maintained, demonstrating a highly stabilizing effect due to the steric demand of the ITr ligand, which protects the metal center from further ligand association. In addition, complexes 1-3 and 8-11 show long-lived luminescence from triplet excited states in the solid state at room temperature, according to our photophysical studies. Our quantum chemical density functional theory/multireference configuration interaction (DFT/MRCI) calculations reveal that the phosphorescence of 8 originates from a locally excited triplet state on the bdt ligand. They further suggest that the phenyl substituents of ITr are photochemically not innocent but can coordinate to the electron-deficient metal center of this trigonal complex in the excited state.

Intercalation of Ionic Liquids into LDH Structures for Microwave-Accelerated Polymerizations.

Microwave-accelerated ring-opening polymerization (ROP) of cyclic esters catalyzed by ionic liquid (IL) anions, intercalated into layered double hydroxides (LDHs), has been recently described as a fast and environmentally friendly synthetic way to prepare biodegradable polyester/LDH nanocomposites. However, to observe this synergistic catalytic effect between microwaves and IL anions and to achieve a homogeneous structure of the final polymer nanocomposite, the IL anions must be efficiently intercalated inside the LDH structure. Herein, we investigate the effects of various metal compositions of M2+/Al3+ LDHs (M = Mg, Co, and Ca) and different LDH synthetic routes (one-step direct coprecipitation, two-step coprecipitation/anion exchange, and two-step urea/anion exchange) on the intercalation efficiency of trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate IL. The most effective IL anion intercalation was observed for Ca2+/Al3+ LDH prepared using the two-step method consisting of coprecipitation and subsequent anion exchange. After optimization, this synthetic pathway led to the production of LDHs with intercalated IL anions and a reduced amount of intercalated water (<0.6 wt %). The catalytic ability of thus optimized LDH particles was demonstrated on the microwave-assisted ROP of ε-caprolactone, showing rapid progress of polymerization. Within minutes, the polycaprolactones with an average molecular mass in the range of 20 000-50 000 g/mol containing fully delaminated and exfoliated LDH nanoparticles were obtained.

Fast and Tunable Phosphorescence from Organic Ionic Crystals.

Crystalline diphosphonium iodides [MeR2 P-spacer-R2 Me]I with phenylene (1, 2), naphthalene (3, 4), biphenyl (5) and anthracene (6) as aromatic spacers, are photoemissive under ambient conditions. The emission colors (λem values from 550 to 880 nm) and intensities (Φem reaching 0.75) are defined by the composition and substitution geometry of the central conjugated chromophore motif, and the anion-π interactions. Time-resolved and variable-temperature luminescence studies suggest phosphorescence for all the titled compounds, which demonstrate observed lifetimes of 0.46-92.23 µs at 297 K. Radiative rate constants kr as high as 2.8×105  s-1 deduced for salts 1-3 were assigned to strong spin-orbit coupling enhanced by an external heavy atom effect arising from the anion-π charge-transfer character of the triplet excited state. These rates of anomalously fast metal-free phosphorescence are comparable to those of transition metal complexes and organic luminophores that utilize triplet excitons via a thermally activated delayed fluorescence mechanism, making such ionic luminophores a new paradigm for the design of photofunctional and responsive molecular materials.

Mechano-Stimulus and Environment-Dependent Circularly Polarized TADF in Chiral Copper(I) Complexes and Their Application in OLEDs.

Molecular emitters that combine circularly polarized luminescence (CPL) and high radiative rate constants of the triplet exciton decay are highly attractive for electroluminescent devices (OLEDs) or next-generation photonic applications, such as spintronics, quantum computing, cryptography, or sensors. However, the design of such emitters is a major challenge because the criteria for enhancing these two properties are mutually exclusive. In this contribution, we show that enantiomerically pure {Cu(CbzR)[(S/R)-BINAP]} [R = H (1), 3,6-tBu (2)] are efficient thermally activated delayed fluorescence (TADF) emitters with high radiative rate constants of kTADF up to 3.1 × 105 s-1 from 1/3LLCT states according to our temperature-dependent time-resolved luminescence studies. The efficiency of the TADF process and emission wavelengths are highly sensitive to environmental hydrogen bonding of the ligands, which can be disrupted by grinding of the crystalline materials. The origin of this pronounced mechano-stimulus photophysical behavior is a thermal equilibrium between the 1/3LLCT states and a 3LC state of the BINAP ligand, which depends on the relative energetic order of the excited states and is prone to inter-ligand C-H···π interactions. The copper(I) complexes are also efficient CPL emitters displaying exceptional dissymmetry values glum of up to ±0.6 × 10-2 in THF solution and ±2.1 × 10-2 in the solid state. Importantly for application in electroluminescence devices, the C-H···π interactions can also be disrupted by employing sterically bulky matrices. Accordingly, we have investigated various matrix materials for successful implementation of the chiral copper(I) TADF emitters in proof-of-concept CP-OLEDs.

An Air- and Moisture-stable Zinc(II) Carbene Dithiolate Dimer Showing Fast Thermally Activated Delayed Fluorescence and Dexter Energy Transfer Catalysis.

A dimeric ZnII carbene complex featuring bridging and chelating benzene-1,2-dithiolate ligands is highly stable towards air and water. The donor-Zn-acceptor structure leads to visible light emission in the solid state, solution and polymer matrices with λmax between 577-657 nm and, for zinc(II) complexes, unusually high radiative rate constants for triplet exciton decay of up to kr =1.5×105  s-1 at room temperature. Variable temperature and DFT/MRCI studies show that a small energy gap between the 1/3 LL/LMCT states of only 79 meV is responsible for efficient thermally activated delayed fluorescence (TADF). Time-resolved luminescence and transient absorption studies confirm the occurrence of long-lived, dominantly ligand-to-ligand charge transfer excited states in solution, allowing for application in Dexter energy transfer photocatalysis.

Ultra-Long Lived Luminescent Triplet Excited States in Cyclic (Alkyl)(amino)carbene Complexes of Zn(II) Halides.

The high element abundance and d10 electron configuration make ZnII -based compounds attractive candidates for the development of novel photoactive molecules. Although a large library of purely fluorescent compounds exists, emission involving triplet excited states is a rare phenomenon for zinc complexes. We have investigated the photophysical and -chemical properties of a series of dimeric and monomeric ZnII halide complexes bearing a cyclic (alkyl)(amino)carbene (cAAC) as chromophore unit. Specifically, [(cAAC)XZn(µ-X)2 ZnX(cAAC)] (X=Cl (1), Br (2), I (3)) and [ZnX2 (cAAC)(NCMe)] (X=Br (4), I (5)) were isolated and fully characterized, showing intense visible light photoluminescence under UV irradiation at 297 K and fast photo-induced transformation. At 77 K, the compounds exhibit improved stability allowing to record ultra-long lifetimes in the millisecond regime. DFT/MRCI calculations confirm that the emission stems from 3 XCT/LEcAAC states and indicate the phototransformation to be related to asymmetric distortion of the complexes by cAAC ligand rotation. This study enhances our understanding of the excited state properties for future development and application of new classes of ZnII phosphorescent complexes.

Coordination capabilities of bis-(2-pyridyl)amides in the field of divalent germanium, tin and lead compounds.

The reactivity of two lithium amides derived from bis-(2-pyridyl)amine (dpa)H or its methyl-substituted congener bis-(6-methyl-2-pyridyl)amine (Me-dpa)H, i.e. (dpa)Li (1) and (Me-dpa)Li (2), toward ECl2 (where E = Ge (dioxane complex) and Sn) is reported. This study produced both heteroleptic complexes (dpa)GeCl (3), [(dpa)SnCl]2 (4), and (Me-dpa)GeCl (5) and homoleptic complexes (dpa)2E (E = Ge (6) or Sn (7)) and (Me-dpa)2E (E = Ge (8) or Sn (9)). The structures of all complexes were established by single-crystal X-ray diffraction analysis showing significant differences depending on the E atom and ligand used. By contrast, in solution, the majority of compounds showed a fluxional behaviour as demonstrated by the NMR study. Finally, it turned out that the Me-dpa ligand, unlike dpa, is able to form ate complexes [(Me-dpa)3E]Li (E = Ge (10), Sn (11) or Pb (12)), whose structures were determined by single-crystal X-ray diffraction analysis. This study revealed the formation of two isomers for Ge and Sn complexes depending on the coordination preference of the lithium atom being coordinated either by nitrogen donors (10-12) or solely by the Ge or Sn electron lone pair (10a and 11a). Furthermore, the NMR experiments proved that the germanium complex 10 exhibits only limited stability in solution and decomposes to germylene 8 and lithium amide 2.

Cyclopentadienyl-Based Anticancer Drugs: Improvement of Cytotoxic Activity through Functionalisation of the π Ligand.

Cytotoxic complexes containing molybdenum are widely studied as a potential substitution for commercially used drugs that often suffer from pronounced side effects and cellular resistance. Compounds of the type [(η5 -Cp')Mo(CO)2 (N,N L)][BF4 ], where Cp is cyclopentadienyl and N,N L is a bidentate ligand, are well known for their strong anticancer activity. It is a generally accepted paradigm that the nature of the coordinated N,N L ligand has a major impact on the cytotoxicity. In this study, a series of new functionalised Cp complexes of molybdenum was synthesised from derivatised fulvenes as π-ligand precursors. Indeed, the coordination sphere's modulation by various N,N-chelating ligands afforded species active toward leukemic cell line MOLT-4 with IC50 values depending on the character of the N,N-chelator used. However, following study clearly showed that functionalisation of the Cp ring with an amine moiety considerably improved cytotoxicity. These results are of crucial importance for the future design of highly active cytotoxic drugs, as modification of cyclopentadienyl is believed to have a minor effect on biological activity.

Salt-washed graphene oxide and its cytotoxicity.

The carbon nanomaterials and congeners, e.g., graphene or graphene oxide (GO), dispose of numerous unique properties, which are not necessarily intrinsic but might be related to a content of impurities. The oxidation step of GO synthesis introduces a considerable amount of metallic species. Therefore, large-scale purification is an actual scientific challenge. Here we describe new purification technique (salt­washing), which is based on three consecutive steps: (a) aggregation of GO sheets with NaCl (b) washing of the aggregates and (c) removing of the salt to afford purified GO (swGO). The considerably improved purity of swGO was demonstrated by ICP and EPR spectroscopy. The microscopic methods (TEM with SEAD, AFM) proved that the salt-washing does not affect the morphology or concentration of defects, showing the aggregation of GO with NaCl is fully reversible. The eligibility of swGO for biomedical applications was tested using fibroblastic cell cultures. The determined IC50 values clearly show a strong correlation between the purity of samples and cytotoxicity. Although the purification decreases cytotoxicity of GO, the IC50 values are still low proving that cytotoxic effect is not only impurities-related but also an intrinsic property. These findings may represent a serious limitation for usage of GO in biomedical applications.

Enhanced cytotoxicity of indenyl molybdenum(ii) compounds bearing a thiophene function.

A series of six indenyl molybdenum compounds bearing a thiophenyl function in the side chain were prepared and characterized by analytical and spectroscopic methods. The structures of [(η5-C9H6CH2C4H3S)(η3-C3H5)Mo(CO)2] and [(η5-C9H6CH2C4H3S)Mo(CO)2(bpy)][BF4] were determined by single-crystal X-ray diffraction. The compounds bearing N,N-chelating ligands exhibit increased cytotoxic activity against human leukemia cell lines MOLT-4; up to two orders of magnitude lower IC50 values were observed compared to analogues with unsubstituted indenyl, which clearly demonstrates the strong effect of the indenyl ligand modification on the biological activity of the molybdenum(ii) compounds. The highest cytostatic potential was observed for the complex bearing 4,7-diphenyl-1,10-phenanthtoline [(η5-C9H6CH2C4H3S)Mo(CO)2(Ph2phen)][BF4] with IC50 (MOLT-4) = 0.19 ± 0.02 µM. Detailed regulation of the molecular and cellular mechanism by this derivative was investigated on the lung carcinoma cell line A549 and compared with the lung fibroblast cell line MRC-5. Rather unusual differences in the effects on tumor and non-tumor cell lines provide a unique insight into the cytostatic action of molybdenum(ii) complexes.

Propene complexes of molybdenum and tungsten stabilized by intramolecular coordination of the 1-(quinol-8-yl)indenyl ligand.

We report herein a new class of mixed propene-indenyl complexes of molybdenum and tungsten stabilized by a strong N→M intramolecular coordination. The complexes [{η5:κN-1-(C9H6N)C9H6}(η2-C3H6)M(CO)2][BF4] (M = Mo, W) were obtained in nearly quantitative yields by the protonation of the η3-allyl ligand in compounds [(η3-C3H5){η5-1-(C9H6N)C9H6}M(CO)2] (M = Mo, W). In contrast to known η2-alkene molybdenum and tungsten compounds, the species presented here are easily isolated in the solid state. The tungsten compound [{η5:κN-1-(C9H6N)C9H6}(η2-C3H6)W(CO)2][BF4] is stable at room temperature, and its structure was unambiguously confirmed by X-ray diffraction. The reactivity of both propene complexes toward several monodentate donors was examined. In the case of dimethyl sulfide, ligand exchange takes place to afford [{η5:κN-1-(C9H6N)C9H6}M(CO)2(SMe2)][BF4] (M = Mo, W) while acetonitrile induces η5→η3 haptotropic rearrangement to give [{η3:κN-1-(C9H6N)C9H6}M(CO)2(NCMe)2][BF4] (M = Mo, W).