270 research outputs found
Cytotoxic Activities of Bis-cyclometalated Iridium(III) Complexes Containing Chloro-substituted kappa N-2-terpyridines
The synthesis and characterization of two new bis-cyclometalated compounds [Ir(ptpy)(2)(kappa N-2-terpy-C6H4Cl-p)]PF6 [terpy-C6H4Cl-p=4'-(4-chlorophenyl)-2,2':6',2''-terpyridine, (1)], and [Ir(ptpy)(2)(kappa N-2-terpy-Cl)]PF6 [terpy-Cl=4'-chloro-2,2':6',2''-terpyridine, (2);ptpy=2-(p-tolyl)pyridinato)] are described. The molecular structures of compounds 1 and 2 in the crystal were determined by single-crystal X-ray diffraction. 1 crystallized from dichloromethane/methanol/iso-hexane in the monoclinic space group P2/(n) and 2 from the same mixture of solvents in the triclinic space group P(-)1. Photophysical investigations on 1 and 2 revealed broad unstructured luminescence in the red spectral region with the emission maxima in dichloromethane at 620 and 630 nm respectively. To explore cytotoxic properties of compounds 1 and 2, a colorimetric assay (MTT assay) against prominent cancer cell lines, MCF-7 and HT-29, was performed. The determined IC50 values are in the low micromolar range (2-3 mu M). In comparison to cisplatin, the tested complexes 1 and 2 exhibit up to >20-fold (MCF-7) and >40-fold (HT-29) increase in biological activity
Highly efficient thermally activated fluorescence of a new rigid Cu(I) complex [Cu(dmp)(phanephos)]+
The rigid [Cu(dmp)(phanephos)]+ complex displays a high luminescence quantum yield of 80% at ambient temperature. In contrast to the long-lived phosphorescence of 240 ÎŒs at T < 120 K with a radiative rate of kr = 3 Ă 103 sâ1, the ambient-temperature emission represents a thermally activated delayed fluorescence (DF) with a decay time of only 14 ÎŒs and a radiative rate of kr(DF) = 6 Ă 104 sâ1. Evidence for the involvement of the excited singlet state in the emission process is presented. This material has high potential to be applied in efficient OLEDs taking advantage of the singlet harvesting mechanism
Designer Reagents for Mass Spectrometry-Based Proteomics: Clickable Cross-Linkers for Elucidation of Protein Structures and Interactions
We present novel homobifunctional amine-reactive clickable cross-linkers (CXLs) for investigation of three-dimensional protein structures and proteinâprotein interactions (PPIs). CXLs afford consolidated advantages not previously available in a simple cross-linker, including (1) their small size and cationic nature at physiological pH, resulting in good water solubility and cell-permeability, (2) an alkyne group for bio-orthogonal conjugation to affinity tags via the click reaction for enrichment of cross-linked peptides, (3) a nucleophilic displacement reaction involving the 1,2,3-triazole ring formed in the click reaction, yielding a lock-mass reporter ion for only clicked peptides, and (4) higher charge states of cross-linked peptides in the gas-phase for augmented electron transfer dissociation (ETD) yields. Ubiquitin, a lysine-abundant protein, is used as a model system to demonstrate structural studies using CXLs. To validate the sensitivity of our approach, biotin-azide labeling and subsequent enrichment of cross-linked peptides are performed for cross-linked ubiquitin digests mixed with yeast cell lysates. Cross-linked peptides are detected and identified by collision induced dissociation (CID) and ETD with linear quadrupole ion trap (LTQ)-Fourier transform ion cyclotron resonance (FTICR) and LTQ-Orbitrap mass spectrometers. The application of CXLs to more complex systems (e.g., in vivo cross-linking) is illustrated by Western blot detection of Cul1 complexes including known binders, Cand1 and Skp2, in HEK 293 cells, confirming good water solubility and cell-permeability
Pyreneânucleobase conjugates: synthesis, oligonucleotide binding and confocal bioimaging studies
Fluorescent pyreneâlinkerânucleobase (nucleobase = thymine, adenine) conjugates with carbonyl and hydroxy functionalities in the linker were synthesized and characterized. X-ray single-crystal structure analysis performed for the pyreneâC(O)CH2CH2âthymine (2) conjugate reveals dimers of molecules 2 stabilized by hydrogen bonds between the thymine moieties. The photochemical characterization showed structure-dependent fluorescence properties of the investigated compounds. The conjugates bearing a carbonyl function represent weak emitters as compared to compounds with a hydroxy function in the linker. The self-assembly properties of pyrene nucleobases were investigated in respect to their binding to single and double strand oligonucleotides in water and in buffer solution. In respect to the complementary oligothymidine T10 template in water, compounds 3 and 5 both show a self-assembling behavior according to canonical baseâbase pairing. However, in buffer solution, derivative 5 was much more effective than 3 in binding to the T10 template. Furthermore the adenine derivative 5 binds to the double-stranded (dA)10âT10 template with a self-assembly ratio of 112%. Such a high value of a self-assembly ratio can be rationalized by a triple-helix-like binding, intercalation, or a mixture of both. Remarkably, compound 5 also shows dual staining pattern in living HeLa cells. Confocal microscopy confirmed that 5 predominantly stains mitochondria but it also accumulates in the nucleoli of the cells
Synthesis, structure and photophysical properties of binuclear methylplatinum complexes containing cyclometalating 2-phenylpyridine or benzo{h}quinoline ligands: a comparison of intramolecular PtâPt and ÏâÏ interactions
The binuclear cyclometalated complexes [Pt2Me2(ppy)2(ÎŒ-dppm)], 1a, and [Pt2Me2(bhq)2(ÎŒ-dppm)], 1b, in which ppy = 2-phenylpyridyl, bhq = benzo{h}quinoline and dppm = bis(diphenylphosphino)methane, were synthesized by the reaction of [PtMe(SMe2)(ppy)] or [PtMe(SMe2)(bhq)] with 1/2 equiv of dppm at room temperature, respectively. Complexes 1a and 1b were fully characterized by multinuclear (1H, 31P, 13C, and 195Pt) NMR spectroscopy and were further identified by single crystal X-ray structure determination. A comparison of the intramolecular PtâPt and ÏâÏ interactions in complexes 1a and 1b has been made on the basis of data on crystal structures and wave functions analysis. The binuclear complexes 1a and 1b are luminescent in the solid state, and showing relatively intense orangeâred emissions stemming from 3MMLCT excited states. The reaction of complex 1b with excess MeI gave the binuclear cyclometalated Pt(IV)âPt(IV) complex [Pt2Me4(bhq)2(ÎŒ-I)2], 2. Crystal structure of complex 2 shows intermolecular CâHâŻI and CâHâŻÏ interactions in solid state
TADF Material Design: Photophysical Background and Case Studies Focusing on CuI and AgI Complexes
The development of organic light emitting diodes (OLEDs) and the use of emitting molecules have strongly stimulated scientific research of emitting compounds. In particular, for OLEDs it is required to harvest all singlet and triplet excitons that are generated in the emission layer. This can be achieved using the so-called triplet harvesting mechanism. However, the materials to be applied are based on high-cost rare metals and therefore, it has been proposed already more than one decade ago by our group to use the effect of thermally activated delayed fluorescence (TADF) to harvest all generated excitons in the lowest excited singlet state S1. In this situation, the resulting emission is an S1âS0 fluorescence, though a delayed one. Hence, this mechanism represents the singlet harvesting mechanism. Using this effect, high-cost and strong SOC-carrying rare metals are not required. This mechanism can very effectively be realized by use of CuI or AgI complexes and even by purely organic molecules. In this investigation, we focus on photoluminescence properties and on crucial requirements for designing CuI and AgI materials that exhibit short TADF decay times at high emission quantum yields. The decay times should be as short as possible to minimize non-radiative quenching and, in particular, chemical reactions that frequently occur in the excited state. Thus, a short TADF decay time can strongly increase the material's long-term stability. Here, we study crucial parameters and analyze their impact on the TADF decay time. For example, the energy separation ÎE(S1âT1) between the lowest excited singlet state S1 and the triplet state T1 should be small. Accordingly, we present detailed photophysical properties of two case-study materials designed to exhibit a large ÎE(S1âT1) value of 1000 cmâ1 (120 meV) and, for comparison, a small one of 370 cmâ1 (46 meV). From these studiesâextended by investigations of many other CuI TADF compoundsâwe can conclude that just small ÎE(S1âT1) is not a sufficient requirement for short TADF decay times. High allowedness of the transition from the emitting S1 state to the electronic ground state S0, expressed by the radiative rate kr(S1âS0) or the oscillator strength f(S1âS0), is also very important. However, mostly small ÎE(S1âT1) is related to small kr(S1âS0). This relation results from an experimental investigation of a large number of CuI complexes and basic quantum mechanical considerations. As a consequence, a reduction of Ï(TADF) to below a few ÎŒs might be problematic. However, new materials can be designed for which this disadvantage is not prevailing. A new TADF compound, Ag(dbp)(P2-nCB) (with dbp=2,9-di-n-butyl-1,10-phenanthroline and P2-nCB=bis-(diphenylphosphine)-nido-carborane) seems to represent such an example. Accordingly, this material shows TADF record properties, such as short TADF decay time at high emission quantum yield. These properties are based (i) on geometry optimizations of the AgI complex for a fast radiative S1âS0 rate and (ii) on restricting the extent of geometry reorganizations after excitation for reducing non-radiative relaxation and emission quenching. Indeed, we could design a TADF material with breakthrough properties showing Ï(TADF)=1.4 ÎŒs at 100 % emission quantum yield. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinhei
Phosphane tuning in heteroleptic [Cu(N^N)(P^P)]+ complexes for light-emitting electrochemical cells
The synthesis and characterization of five [Cu(P^P)(N^N)][PF6] complexes in which P^P = 2,7-bis(tert-butyl)-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (tBu2xantphos) or the chiral 4,5-bis(mesitylphenylphosphino)-9,9-dimethylxanthene (xantphosMes2) and N^N = 2,2'-bipyridine (bpy), 6-methyl-2,2'-bipyridine (6-Mebpy) or 6,6'-dimethyl-2,2'-bipyridine (6,6'-Me2bpy) are reported. Single crystal structures of four of the compounds confirm that the copper(I) centre is in a distorted tetrahedral environment. In [Cu(xantphosMes2)(6-Mebpy)][PF6], the 6-Mebpy unit is disordered over two equally populated orientations and this disorder parallels a combination of two dynamic processes which we propose for [Cu(xantphosMes2)(N^N)]+ cations in solution. Density functional theory (DFT) calculations reveal that the energy difference between the two conformers observed in the solid-state structure of [Cu(xantphosMes2)(6-Mebpy)][PF6] differ in energy by only 0.28 kcal molâ1. Upon excitation into the MLCT region (λexc = 365 nm), the [Cu(P^P)(N^N)][PF6] compounds are yellow to orange emitters. Increasing the number of Me groups in the bpy unit shifts the emission to higher energies, and moves the Cu+/Cu2+ oxidation to higher potentials. Photoluminescence quantum yields (PLQYs) of the compounds are low in solution, but in the solid state, PLQYs of up to 59% (for [Cu(tBu2xantphos)(6,6'-Me2bpy)]+) are observed. Greatly increased excited-state lifetimes at low temperature are consistent with the complexes exhibiting thermally activated delayed fluorescence (TADF). This is supported by the small energy difference calculated between the lowest-energy singlet and triplet excited states (0.17-0.25 eV). The compounds were tested in simple bilayer light-emitting electrochemical cells (LECs). The optoelectronic performances of complexes containing xantphosMes2 were generally lower with respect to those with tBu2-xantphos, which led to bright and efficient devices. The best performing LECs were obtained for the complex [Cu(tBu2xantphos)(6,6'-Me2bpy)][PF6] due to the increased steric hindrance at the N^N ligand resulting in higher PLQY
Copper and gold cyclic (alkyl)(amino)carbene complexes with sub-microsecond photoemissions: Structure and substituent effects on redox and luminescent properties
Copper and gold halide and pseudo-halide complexes stabilized by methyl-, ethyl- and adamantyl-substituted cyclic (alkyl)(amino)ÂŹcarbene (CAAC) ligands are mostly linear monomers in the solid state, without aurophilic Au···Au interactions. (Et2L)CuCl shows the highest photoluminescence quantum yield (PLQY) in the series, 70%. The photoemissions of Me2L and Et2L copper halide complexes show S1 â S0 fluorescence on the ns time scale, in agreement with theory, as well as a minor long-lived emission. Monomeric (Me2L)CuNCS is a white emitter, while dimeric [(Et2L)Cu(”-NCS)]2 shows intense yellow emission with a PLQY of 49%. The reaction of (AdL)MCl (M = Cu or Au) with phenols ArOH (Ar = Ph, 2,6-F2C6H3, 2,6-Me2C6H3, 3,5-But2C6H3, 2-But-5-MeC6H3, 2-pyridyl), thiophenol, or aromatic amines H2NAr' (Ar' = Ph, 3,5-(CF3)2C6H3, C6F5, 2-py) afforded the corresponding phenolato, thiophenolato and amido complexes. Whereas the emission wavelengths are only marginally affected by the ring substitution pattern, the PL intensities respond sensitively to the presence of substituents in ortho or meta position. In gold aryloxides PL is controlled by steric factors, with strong luminescence in compounds with Au-O-C-C torsion angles <50. Calculations confirm the dependence of oscillator strength on the torsion angle, as well as the inter-ligand charge transfer nature of the emission. The HOMO/LUMO energy levels were estimated based on first reduction and oxidation potentials
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