Metal-to-ligand Charge Transfer Transitions Research Articles

Copper(I) photosensitizer-silica nanoparticle assembly towards enhanced aqueous photoluminescence

Harnessing the luminescence potential of Cu(I) complexes in aqueous media is typically hindered by their poor photostability and altered properties. Here, we report the synthesis, engineering and morphological characterization of a hydrophobic homoleptic copper(I) complex entrapped into silica nanoparticles, Cu-I@SiO2 (where “Cu-I” designates [Cu(2,9-diiodo-1,10-phenanthroline)2]+), as a promising stabilisation strategy towards water-compatible, Cu(I) complex-based luminescence. The polyether chain-decorated nano-objects are spherical with an average diameter of ca. 10.8 ± 1.9 nm. Upon dispersion in water, clear solution-like suspensions were obtained. Significantly, the aqueous suspensions photo-luminesce (Φem = 5×10-4) upon excitation through the Metal-to-Ligand Charge-Transfer transition (MLCT) of the embedded copper(I) complexes. In contrast, the corresponding silica-free molecular complex dissolved in an aqueous environment revealed fully quenched emission. Finally, the use of Cu-I@SiO2 suspensions as luminescent probes is reported, first by assessing their potential use as electrochemiluminescent probes, and second by monitoring the photoluminescence from Cu-I@SiO2 in the presence of whole blood.

Enhanced Visible Light Absorption in Heteroleptic Cuprous Phenanthrolines.

This work presents a series of Cu(I) heteroleptic 1,10-phenanthroline chromophores featuring enhanced UVA and visible-light-harvesting properties manifested through vectorial control of the copper-to-phenanthroline charge-transfer transitions. The molecules were prepared using the HETPHEN strategy, wherein a sterically congested 2,9-dimesityl-1,10-phenanthrolne (mesPhen) ligand was paired with a second phenanthroline ligand incorporating extended π-systems in their 4,7-positions. The combination of electrochemistry, static and time-resolved electronic spectroscopy, 77 K photoluminescence spectra, and time-dependent density functional theory calculations corroborated all of the experimental findings. The model chromophore, [Cu(mesPhen)(phen)]+ (1), lacking 4,7-substitutions preferentially reduces the mesPhen ligand in the lowest energy metal-to-ligand charge-transfer (MLCT) excited state. The remaining cuprous phenanthrolines (2-4) preferentially reduce their π-conjugated ligands in the low-lying MLCT excited state. The absorption cross sections of 2-4 were enhanced (εMLCTmax = 7430-9980 M-1 cm-1) and significantly broadened across the UVA and visible regions of the spectrum compared to 1 (εMLCTmax = 6494 M-1 cm-1). The excited-state decay mechanism mirrored those of long-lived homoleptic Cu(I) phenanthrolines, yielding three distinguishable time constants in ultrafast transient absorption experiments. These represent pseudo-Jahn-Teller distortion (τ1), singlet-triplet intersystem crossing (τ2), and the relaxed MLCT excited-state lifetime (τ3). Effective light-harvesting from Cu(I)-based chromophores can now be rationalized within the HETPHEN strategy while achieving directionality in their respective MLCT transitions, valuable for integration into more complex donor-acceptor architectures and longer-lived photosensitizers.

Electronic structure of a dinuclear ruthenium(II)-2,2’-bipyridine complex

The dinuclear polypyridyl complex [{Ru(bipy)2}2(µ-L)](PF6)4, where bipy = 2,2'-bipyridine and L = 2,6-bis[(1,10-phenantroline-5-amine)methyl]pyridine, was prepared and characterized by UV-Vis and infrared spectroscopy. Geometry optimization revealed the possibility of three conformers, and time-dependent density functional theory calculations provided access to the correct excited state composition and unambiguous assignment of the characteristic metal-ligand charge transfer transitions.

Coexistence of Three Different Spin States in a Cyanido-Bridged Trinuclear Iron(III) Complex with an Unusual FeIII to Ligand Charge Transfer.

We report a trinuclear iron(III) cyanido-bridged complex trans-[CpMe3 FeIII (dppe)(CN)]2 [FeIII (LN4 )][PF6 ]4 (2[PF6 ]4 ) as the oxidation product of binuclear complex [CpMe3 (dppe)FeII CN-FeIII (LN4 )][PF6 ] (1[PF6 ]) (CpMe3 =1, 2, 4-trimethyl-1,3-cyclo-pentadienyl, dppe=1,2-bis(diphenylphosphino)ethane, LN4 =pentane-2,4-dione-bis(S-methylisothiosemicarbazonato). Complex 1[PF6 ] possesses an intermediate-spin five-coordinated FeIII (S=3/2) which couples antiferromagnetically to the π-radical ligand (L⋅N4 )2- and shows a LMCT (ligand to metal charge transfer) transition from (L⋅N4 )2- to FeIII and the FeII →FeIII MMCT transition. Upon oxidation of 1[PF6 ], (L⋅N4 )2- loses one electron to be the strong electron-attracting ligand (LOx N4 )- and the intermediate-spin five-coordinated FeIII (S=3/2) becomes a low-spin six-coordinated FeIII (S=1/2) in 2[PF6 ]4 . Also interestingly, 2[PF6 ]4 presents the coexistence of three different spin states (one S=3/2 and two S=1/2) and an uncommon FeIII →(LOx N4 )- MLCT transition, confirmed by the experimental results and supported by the TDDFT calculations.

Isocyanide Ligands Promote Ligand-to-Metal Charge Transfer Excited States in a Rhenium(II) Complex.

A metal-to-ligand charge transfer with mixed intraligand character is observed for the rhenium hexakisarylisocyanide complex [Re(CNAr)6]PF6 (CNAr = 2,6-dimethylphenylisocyanide, λmax = 300 nm). Upon oxidation to [Re(CNAr)6](PF6)2, the dominant low energy optical transition is a ligand-to-metal charge transfer (LMCT) mixed with intraligand transitions (λmax = 650 nm). TD-DFT was used to identify the participating ligand-based orbitals in the LMCT transition, revealing that the majority of the donor orbital is based on the aryl ring (85%) as opposed to the CN bond (14%). For both [Re(CNAr)6]+ and [Re(CNAr)6]2+, structural characterization by X-ray diffraction reveals deviations from Oh geometry at the central Re ion, with larger reduction in symmetry observed for Re(II). For [Re(CNAr)6]+, these structural changes lead to a broadening of the strong ν(C≡N) stretch (2065 cm-1), as the degeneracy of the T1u IR-active mode is broken. Furthermore, a shoulder is observed for this ν(C≡N) stretch, resulting from deviation of the C-N-Ar bond from linearity. By contrast, [Re(CNAr)6]2+ has two weak bands in the ν(C≡N) region (2065 and 2121 cm-1). DFT calculations indicate that reduction of symmetry at the central rhenium ion manifests in the decrease in intensity and the observed split of the ν(C≡N) band. Stability of both complexes are limited by light-induced decomposition where Re(I) dissociates a isocyanide ligand upon irradiation and Re(II) absorbance decays under ambient light. These data provide new insights to the electronic structure of [Re(CNAr)6]2+, enhancing our understanding of LMCT excited states and the versatility of isocyanide ligands.

Circularly Polarized Luminescence of Palladium(0) Complexes Bearing Chiral Diphosphines

Four palladium(0) complexes bearing diphosphine ligands were prepared and their chiroptical properties were studied. The structures of two new complexes were elucidated by X-ray crystallography. These complexes show photoluminescence in solution, with quantum yields of 0.4–42%, as well as circular dichroism (CD) at the metal–ligand charge transfer transition bands. The three complexes bearing biaryl phosphine ligands exhibit circularly polarized luminescence of moderate intensities; the sign and the dissymmetry factors of which coincide with the CD spectra.

Synthesis, structure and photoluminescence of Cu(I) complexes containing new functionalized 1,2,3-triazole ligands.

The reaction of a triazole ligand, 2-(1H-1,2,3-triazol-4-yl)pyridine (L1), with 2-bromopyridine afforded three new ligands, 2,2'-(1H-1,2,3-triazole-1,4-diyl)dipyridine (L2), 2,2'-(2H-1,2,3-triazole-2,4-diyl)dipyridine (L3) and 2,2'-(1H-1,2,3-triazole-1,5-diyl)dipyridine (L4). A series of luminescent mononuclear copper(I) complexes of these ligands [Cu(Ln)(P^P)](ClO4) [n = 1, P^P = (PPh3)2 (1); n = 1, P^P = POP (2); n = 2, P^P = (PPh3)2 (3); n = 2, P^P = POP (4); n = 3, P^P = (PPh3)2 (5); n = 3, P^P = POP (6); n = 4, P^P = (PPh3)2 (9); n = 4, P^P = POP (10)] have been obtained from the reaction of Ln with [Cu(MeCN)4]ClO4 in the presence of PPh3 and POP. L3 was also found to form dinuclear compounds [Cu2(L3)(PPh3)4](ClO4)2 (7) and [Cu2(L3)(POP)2](ClO4)2 (8). All of the Cu(I) compounds have been characterized by IR, UV/vis, CV, 1H NMR, and 31P{1H} NMR. The molecular structures of 1-3, 5, and 7 have been further determined by X-ray crystallography. In CH2Cl2 solutions, these Cu(I) complexes exhibit tunable green to orange emissions (563-621 nm) upon excitation at λex = 380 nm. In the solid state, these complexes show intense emissions and it is interesting to note that 1 and 3 are blue-light emitters. Density functional theory (DFT) calculations revealed that the lowest energy electronic transition associated with these complexes predominantly originates from metal-to-ligand charge transfer transitions (MLCT).

9-Phenyl-9-phosphafluorene oxide based organic ligands synthesized via successive SNAr reactions and their symmetric phosphorescent Ir(III) complexes for highly efficient solution-processed OLEDs

Three organic ligands with 9-phenyl-9-phosphafluorene oxide (PhFlPO) group have been synthesized via successive nucleophilic aromatic substitution (SNAr) reactions between dibenzothiophene dioxides and PhPH2-KOH under mild reaction conditions at room temperature. In this way, the novel PhFlPO-type organic ligands can be easily obtained without either highly sensitive Grignard or organolithium reagents of noble metal catalysts. Using these PhFlPO-type organic ligands, cyclometalated Ir(III) phosphorescent complexes with PhFlPO groups have been developed through well-accepted two-step strategy. To the best of our knowledge, these complexes represent the unprecedented examples of symmetric cyclometalated Ir(III) phosphorescent complexes bearing PhFlPO group. It has been found that electron-density on the coordinated carbon atom in the PhFlPO unit can exert a significant influence on the metal-to-ligand charge transfer transition (MLCT) processes and phosphorescent emission behavior of these cyclometalated Ir(III) phosphorescent complexes. In addition, the electroluminescent potential of these new cyclometalated Ir(III) phosphorescent complexes with PhFlPO groups has been characterized in solution-processed organic light-emitting diodes (OLEDs). They can show very impressively high external quantum efficiency (ηext), current efficiency (ηL) and power efficiency (ηP) of 20.0%, 71.7 cd A−1 and 56.1 lm W−1, respectively. These encouraging research results can furnish critical information for developing new PhFlPO-based Ir(III) phosphorescent emitters.

Distinctive Aspects in Aquation, Proton-Coupled Redox, and Photoisomerization Reactions between Geometric Isomers of Mononuclear Ruthenium Complexes with a Large-π-Conjugated Tetradentate Ligand.

Geometric isomers of mononuclear ruthenium(II) complexes, distal-/proximal-[Ru(tpy)(dpda)Cl]+ (d-/p-RuCl, tpy = 2,2':6',2″-terpyridine, dpda = 2,7-bis(2-pyridyl)-1,8-diazaanthracene), were newly synthesized to comprehensively investigate the geometric and electronic structures and distinctive aspects in various reactions between isomers. The ultraviolet (UV)-visible absorption spectra of d-/p-RuCl isomers show intense bands for metal-to-ligand charge transfer (MLCT) at close wavelengths of 576 and 573 nm, respectively. However, time-dependent density functional theory (TD-DFT) calculations suggest that the MLCT transition of d-RuCl involves mainly single transitions to the π* orbital of the dpda ligand in contrast to mixing of the π* orbitals of the dpda and tpy ligands for p-RuCl. The aquation reaction (1.5 × 10-3 s-1) of p-RuCl to yield proximal-[Ru(tpy)(dpda)(OH2)]2+ (p-RuH2O) is faster than that (5.3 × 10-6 s-1) of d-RuCl in D2O/CD3OD (4:1 v/v) by three orders of magnitude, which resulted from the longer Ru-Cl bond by 0.017 Å and the distorted angle (100.2(3)°) of Cl-Ru-N (a nitrogen of dpda, being on a tpy plane) due to the steric repulsion between Cl and dpda for p-RuCl. Electrochemical measurements showed that d-RuH2O undergoes a 2-step oxidation reaction of 1H+-coupled 1e- processes of RuII-OH2/RuIII-OH and RuIII-OH/RuIV═O at pH 1-9, whereas p-RuH2O undergoes a 1-step oxidation reaction of a 2H+-coupled 2e- process of RuII-OH2/RuIV═O in the pH range of pH 1-10. The irreversible photoisomerization from d-RuH2O to p-RuH2O was observed in aqueous solution with an internal quantum yield (Φ) of 5.4 × 10-3% at 520 nm, which is lower compared with Φ = 1.1-2.1% of mononuclear Ru(II) aquo complexes with similar bidentate ligands instead of dpda by three orders of magnitude. This is possibly ascribed to the faster nonradiative decay rate from the excited 3MLCT state to the ground state for d-RuH2O due to the lower π* level of dpda ligands according to the energy-gap law: the rate decreases exponentially with the increasing energy gap.

Influence of electron-donating ability of ligand and pH value on MLCT properties of cyanido-bridged complexes

In this work, one mononuclear complex CH3CNFeII(eq-Py4PzMe2) (1) and two binuclear complexes Cp(dppe)MIICNFeII(eq-Py4PzMe2) (M = Ru 2, Fe 3; Cp = cyclopentadiene, dppe = 1,2-bis(diphenylphosphino)ethane, eq-Py4PzMe2 = 2-(1-(6-(1,1-di(pyridin-2-yl)ethyl)pyridin-2-yl)-1-(pyridin-2-yl)ethyl)pyrazine) were synthesized. Combined with the TDDFT calculations, the metal-to-ligand charge transfer (MLCT) properties of all the compounds were investigated. The results show that for the mononuclear complex, the MLCT originates from FeII to the pyrazine (Pz) component of the eq-Py4PzMe2 ligand. After the substitution of CH3CN in complex 1 by the half-sandwich fragment Cp(dppe)MIICN, the binuclear complexes 2 and 3 exhibit the MLCT transition from the neighboring FeII atom to the Pz component of the eq-Py4PzMe2 together with some contributions from the remote MII. With the increase of the electron-donating ability from CH3CN, Cp(dppe)RuIICN to Cp(dppe)FeIICN, the MLCT transition energy decreases. Furthermore, with the decrease of pH value, all the MLCT absorption bands are significantly redshifted by 160 nm or more, and the extent of these red shifts increases from complex 1 to 2, to 3.

Influence of the electronic effect of an ancillary ligand on MMCT and LMCT in localized cyanide-bridged complexes containing non-innocent ligands.

Mixed-valence (MV) complexes containing non-innocent ligands are excellent models for the investigation of the electron-transfer process. A series of twelve bimetallic cyanide-bridged complexes [CpMen(dppe)RuCNFeLx][A] (A = PF6- or I-, CpMen = alkyl cyclopentadienyl, dppe = 1,2-bis (diphenylphosphino)ethane, and LX = pentane-2,4-dione-bis (S-alkylisothiosemi-carbazonato); n = 0, x = Methyl (Me), Ethyl (Et), n-Propyl (Pr) and n-Butyl (Bu), and A = PF6-, 1Me[PF6], 1Et[PF6], 1Pr[PF6], and 1Bu[PF6]; n = 1, x = Me, Et, Pr, and Bu, and A = PF6-, 2Me[PF6], 2Et[PF6], 2Pr[PF6], and 2Bu[PF6]; n = 5, x = Me, Et, Pr, and Bu, and A = I-, 3Me[I], 3Et[I], 3Pr[I], and 3Bu[I]) have been synthesized and well characterized. The investigations demonstrate that all the cations of the complexes could be described with the basic electronic configuration , in which the fragment could be regarded as being delocalized. The ligand to metal charge transfer (LMCT) transition in the fragment and the low-spin RuII to the intermediate-spin FeIII charge transfer (MMCT) transition have been investigated. The UV-vis-NIR spectral analysis results suggest that the energy of the LMCT transition is lower than that of the MMCT transition due to electron delocalization between the non-innocent ligand and the FeIII ion, which is strongly supported by TDDFT calculations. Furthermore, the RuII → FeIII MMCT energy decreases and the LMCT energy increases with the increasing electron donating ability of the ancillary ligands from Cp, CpMe to CpMe5, but slightly changes with the variation of the ligand Lx from Me, Et, Pr to Bu. Compared to the MMCT energy change, however, the energy of the LMCT from to FeIII in the delocalized moiety is less influenced by the electronic effect of the ancillary ligand or the CpMen(dppe)RuIICN (n = 0, 1 and 5) fragment.

X-ray absorption near-edge spectroscopy of antimony complexed with organic molecules: a theoretical interpretation

The shoulder feature for the white line (Sb K-edge) was ascribed to metal–ligand charge transfer transitions from Sb 1s to the unoccupied states of the carbon chains. Longer distance for charge transfer caused lower intensity of the shoulder peak.

Mechanisms of the Cu(I)-Catalyzed Intermolecular Photocycloaddition Reaction Revealed by Optical and X-ray Transient Absorption Spectroscopies.

The [2 + 2] photocycloaddition provides a simple, single-step route to cyclobutane moieties that would otherwise be disfavored or impossible due to ring strain and/or steric interactions. We have used a combination of optical and X-ray transient absorption spectroscopies to elucidate the mechanism of the Cu(I)-catalyzed intermolecular photocycloaddition reaction using norbornene and cyclohexene as model substrates. We find that for norbornene the reaction proceeds through an initial metal-to-ligand charge transfer (MLCT) state that persists for 18 ns before the metal returns to the monovalent oxidation state. The Cu K-edge spectrum continues to evolve until ∼5 μs and then remains unchanged for the 50 μs duration of the measurement, reflecting product formation and ligand dissociation. We hypothesize that the MLCT transition and reverse electron transfer serve to sensitize the triplet excited state of one of the norbornene ligands, which then dimerizes with the other to give the product. For the case of cyclohexene, however, we do not observe a charge transfer state following photoexcitation and instead find evidence for an increase in the metal-ligand bond strength that persists for several ns before product formation occurs. This is consistent with a mechanism in which ligand photoisomerization is the initial step, which was first proposed by Salomon and Kochi in 1974 to explain the stereoselectivity of the reaction. Our investigation reveals how this photocatalytic reaction may be directed along strikingly disparate trajectories by only very minor changes to the structure of the substrate.

The ligand-to-metal charge transfer excited state of [Re(dmpe)3]2.

The ligand-to-metal charge transfer (LMCT) transitions of [Re(dmpe)3]2+ (dmpe = bis-1,2-(dimethylphosphino)ethane) were interrogated using UV/Vis absorbance spectroscopy, photoluminescence spectroscopy, and time-dependent density functional theory. The solvent dependence of the lowest energy charge transfer transition was quantified; no solvatochromism was observed. TD-DFT calculations reveal the dominant LMCT transition is highly symmetric and delocalized involving all phopshine ligand donors in the charge transfer, providing an understanding for the absence of solvatochromism of [Re(dmpe)3]2+.

DPP based dual-sensing probe for the multi-color detection of toxic Co2+/Sn2+ and CN− ions in water: An electronic eye development

A dual-sensing mechanism probe for the multi-color detection of toxic Co2+/Sn2+ and CN− ions in water based on a diketopyrrolopyrrole (DPP) moiety was designed and successfully synthesized. Colorimetric and fluorimetric methods were used to confirm the sensing performance of the probe. Different colors were achieved for the detecting ions Co2+, Sn2+, and CN−. pink for Co2+, red for Sn2+, and colorless for CN−, denoting high selectivity in the developed probe. A dual-sensing mechanism confirmed for the metal ion the sensing is via complexation resulting in color (different) change through metal to ligand charge-transfer transition (MLCT), and for anion (cyanide), it is through addition reaction with a disconnection in intramolecular charge-transfer transition (ICT). Pre-added selected ions to the different water samples effectively detect different colors. We developed an electronic eye (RGB - Arduino device) for the detection of toxic ions effectively.

Heterologous production and functional characterization of Bradyrhizobium japonicum copper-containing nitrite reductase and its physiological redox partner cytochrome c550.

Two domain copper-nitrite reductases (NirK) contain two types of copper centers, one electron transfer (ET) center of type 1 (T1) and a catalytic site of type 2 (T2). NirK activity is pH-dependent, which has been suggested to be produced by structural modifications at high pH of some catalytically relevant residues. To characterize the pH-dependent kinetics of NirK and the relevance of T1 covalency in intraprotein ET, we studied the biochemical, electrochemical, and spectroscopic properties complemented with QM/MM calculations of Bradyrhizobium japonicum NirK (BjNirK) and of its electron donor cytochrome c550 (BjCycA). BjNirK presents absorption spectra determined mainly by a S(Cys)3pπ → Cu2+ ligand-to-metal charge-transfer (LMCT) transition. The enzyme shows low activity likely due to the higher flexibility of a protein loop associated with BjNirK/BjCycA interaction. Nitrite is reduced at high pH in a T1-decoupled way without T1 → T2 ET in which proton delivery for nitrite reduction at T2 is maintained. Our results are analyzed in comparison with previous results found by us in Sinorhizobium meliloti NirK, whose main UV-vis absorption features are determined by S(Cys)3pσ/π → Cu2+ LMCT transitions.

Bismuth and lead based metal organic frameworks: morphological, luminescence and Brunauer-Emmett-Teller (BET) studies

Abstract Biphenyl-4,4′-dicarboxylic acid (H2BDA) was used as an organic linker to synthesize bismuth and lead based organic frameworks (1 and 2). The structural/morphological studies of these metal organic frameworks (MOFs) were done using UV-Vis, Fourier transform infrared spectroscopy (FT-IR), 1H NMR, energy dispersive spectroscopy (EDXS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and powder X-ray diffraction method. Surface area as determined by Brunauer-Emmett-Teller (BET) studies revealed better N2 gas adsorption for MOF (1) compared to MOF (2). Both these MOFs exhibited good luminescence activity which was attributed to ligand-to-metal charge transfer transitions (LMCT).

Synthesis, crystal structure and optical properties of Anderson-type heteropolyanion with cobalt cations

A sample inorganic A-type Anderson polyoxometalate (POM) (TeMo6) compound formulated as [Co(H2O)6]3[TeMo6O24] is synthesized in aqueous solution by slow evaporation technique. Single-crystal X-ray diffraction analysis reveals that the obtained compound crystallizes in the centrosymmetric hexagonal space group (R-3c) with a formula unit made up of one [TeMo6O24]6− A-type Anderson anion and three [Co(H2O)3]2+ cations. The molecular Hirshfeld surface indicates that the crystal packing is stabilized by H-bonds interactions to generate 3D supramolecular frameworks. Furthermore, some optical properties such as bandgap energy, refractive index, dielectric constant and optical conductivity of the sample are investigated. The large value of refractive index known in the visible region of electromagnetic spectrum (n = 3.5 at 1.8 eV) reveals that this sample can become a promising candidate for visible optical communication devices. The emission fluorescent spectrum in the solid state at room temperature is measured and the decay lifetime curves are obtained by monitoring the ligand-to-metal charge transfer transition (LMCT). The studies of the colorimetric properties of the sample reveal that the color coordinates (x = 0.33667; y = 0.25564) are located in the region of National Television System Committee (NTSC) in the CIE chromaticity chart and the calculated correlated color temperature value (CCT ~ 5085 K) indicates that the optimized compound could be applied as a cool light emission diode.

Efficient TADF-OLEDs with ultra-soluble Copper(I) halide complexes containing non-symmetrically substituted bidentate phosphine and PPh3 ligands

High efficiency copper(I) halide complexes containing rigid diphosphine ligand have attracted much attention. However, rigid bidentate phosphine ligands were rarely reported so far and limited to structural symmetric diphosphines. Here, a series of four-coordinate mononuclear copper(I) halide complexes containing non-symmetrically substituted bidentate phosphine and PPh3 Ligands, CuX(dpts)(PPh3) [dpts = 2-trimethylsilyl-3,4-bis(diphenylphosphine)thiophene, X = I (1), Br (2), Cl (3)] and in comparison to CuX(dppt)(PPh3) [dppt = 3,4-bis(diphenylphosphino)thiophene, X = I (4), Br (5), Cl (6)], were synthesized, and their molecular structures and photophysical properties were investigated. The introduction of trimethylsilyl group into diphosphine ligand, not only greatly improves the solubility of the complexes, but also quantum efficiency, and fine-tunes the emission color as well. These complexes exhibit intense bluegreen to yellowish green emissions in powder state at room temperature and have peak wavelengths at 485–535 nm with microsecond lifetimes (τ = 4.8–48.9 μs, Φ = 0.03–0.52). The emission of the complexes 1–6 mainly originates from MLCT (metal to ligand charge transfer), XLCT (halide to ligand charge transfer) and intraligand transitions. Solution-processed, nondoped and doped devices of complex 2 exhibit yellow green emission with CIE(x,y) of (0.43, 0.51). The nondoped device gives a maximum external quantum efficiency (EQE) of 7.74% and a maximum luminance of 234 cd/m2. These promising results open the door to solution-processed, efficient TADF (thermally activated delayed fluorescence) OLED (organic light-emitting diode) devices with ultra-soluble and abundant copper emitters.

Rhenium(I) polypyridine complexes coordinated to an ethyl-isonicotinate ligand: Luminescence and in vitro anti-cancer studies

In this work, fac-[Re(et-isonic)(NN)(CO)3]+ complexes, et-isonic = ethyl-isonicotinate, NN = 1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (Ph2phen), 4,7-dichloro-1,10-phenanthroline (Cl2phen) or 4,7-dimethyl-1,10-phenanthroline (Me2phen), were synthesized to combine different substituent groups at coordinate phen ligand along with the coordination of a nicotinic acid derivative aiming the modulation of the photophysical and lipophilic properties. The electronic absorption spectra profile can be divided into two main regions: the high-energy region ascribed to the intraligand transition (IL), and the low-energy region assigned to the metal-to-ligand charge transfer transition (MLCT). Additionally, the complexes exhibited 3MLCT emission, sensitive to the nature of NN ligand, which can be used to photosensitize the generation of singlet oxygen as well as to localize them into the cell. The lipophilicity of the complexes increases as the substituent at coordinated phen ligand was changed from hydrogen to phenyl and these results reflected also in the same trend observed for the cytotoxicity results, in the absence of light, using breast cancer (MCF-7) and melanoma (SkMel-147 and SkMel-29) cell lines. In addition, the flow cytometry assay along with the Western Blotting analyses showed an overexpression on pro caspase-9, suggesting a Caspase proteolytic cascade through the intrinsic pathway in the apoptosis as the mechanism of action. In spite of the Re(I) complexes were capable of generating singlet oxygen in the presence of light, they were very effective in killing the cells by a different mechanism of action in the absence of light. Thus, these results provided a better understanding of the mechanism of anticancer action and highlight the potential application of rhenium(I) complexes in the development of a novel therapy process.