RESUMEN

In the present work, several coumarin-3-carboxamides with different azacrown ether moieties were designed and tested as potential luminescent sensors for metal ions. The derivative containing a 1-aza-15-crown-5 as a metal chelating group was found to yield the strongest response for Ca2+ and Pb2+, exhibiting an eight- and nine-fold emission increase, respectively, while other cations induced no changes in the optical properties of the chemosensor molecule. Job's plots revealed a 1:1 binding stoichiometry, with association constants of 4.8 × 104 and 8.7 × 104 M-1, and limits of detection of 1.21 and 8.04 µM, for Ca2+ and Pb2+, respectively. Computational studies suggest the existence of a PET quenching mechanism, which is inhibited after complexation with each of these two metals. Proton NMR experiments and X-ray crystallography suggest a contribution from the carbonyl groups in the coumarin-3-carboxamide fluorophore in the coordination sphere of the metal ion.

RESUMEN

1,8-Naphthalimides (NIs) represent a class of organic dyes with interesting optical properties that has been extensively explored in the last decades in lighting devices, chemosensors, optical probes or medicinal chemistry. However, despite their remarkable potential, reports on organometallic dyes bearing NIs are scarce and virtually inexistent regarding palladium(II) complexes. Herein, we report the synthesis of NIs bearing phosphine and amine chelating moieties and the characterization of their optical properties both as single molecules and when complexed on Pd(II) ions. It is shown that the introduction of phosphine moieties in the naphthalimide core results in a marked increase in non-radiative processes, leading to a significant reduction of the emission efficiency and lifetime of these dyes, compared to amine-bearing counterparts. The complexation to Pd(II) sequesters the electronic contribution of chelating moieties, with complexes assuming an optical behavior similar to that of unsubstituted 1,8-naphthalimide. The complexation significantly increases the acidity of chelating secondary amines, giving rise to an unexpected intramolecular reaction that results in the formation of a novel 1,8-naphthalimide dye bearing a cyclic phosphorylamide moiety. The new dye exhibits good emission quantum yield, long fluorescence lifetime and sensitivity to basic media, evidencing potential for application in optical imaging and sensing scenarios.

RESUMEN

Here we discuss the influence of two different cations on the emissive properties of the highly emissive [Eu(fod)4]- anion. The studied Eu(III) salts were [C16Pyr][Eu(fod)4] (1), and the previously reported [Chol][Eu(fod)4]. C16Pyr stands for N-cetylpyridinium, Chol for cholinium and fod for 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate. 1 is classified as ionic liquid, with melting point close to 60 °C, and presented a luminescence quantum yield of (ϕ) 100%. Ultrabright emissive photopolymers were obtained for the first time using polysulfone as the host matrix. The films were prepared with incorporation of 10% (w/w) of 1 and [Chol][Eu(fod)4] in the polymeric matrix, which improved its thermal stability. Additionally, the luminescence of CholEu(fod)4/PSU presented a strong temperature dependence with a ratiometric thermal behavior.

RESUMEN

An emissive europium(III) complex [C2 mim][Eu(fod)4 ] (1; C2 mim=1-ethyl-3-methyl-imidazolium; fod=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate) was prepared. The complex shows ratiometric thermal behaviour up to 155 °C. These unusual temperature-dependent properties arise from a solid-solid phase transition that promotes increased contact between the anion and the cation, affecting the emission profile of the emissive anion in two different ratiometric relations. A ultrabright and flexible emissive photopolymer film was obtained using polysulfone (PSU) as the host matrix of 10 % (w/w) of 1, that also induced changes on the lanthanide emissive profile with temperature. A temperature-responsive luminescent film 1/PSU is sensitivr to heating between 100 and 155 °C. Also, the emission lifetime of 1 was not affected by confinement in PSU, while its emission quantum yield was reduced from 82 to 59 %.

RESUMEN

A new fluorescent chemosensor for copper (II) and subsequent anion sensing was designed and fully characterized. The sensor consisted of a 1,8-naphthalimide core, bearing two terminal dipicolylamine (DPA) receptor units for binding metal cations, and an ethoxyethanol moiety for enhanced water solubility. The DPA units are connected to position 4 of the fluorophore via a triazine-ethylenediamine spacer. Fluorescence titration studies of the chemosensor revealed a high selectivity for Cu2+ over other divalent ions, the emissions were strongly quenched upon binding, and a stability constant of 5.52 log units was obtained. Given the distance from DPA chelating units and the fluorophore, quenching from the Cu2+ complexation suggests an electron transfer or an electronic energy transfer mechanism. Furthermore, the Cu2+-sensor complex proved to be capable of sensing anionic phosphate derivatives through the displacement of the Cu2+ cation, which translated into a full recovery of the luminescence from the naphthalimide. Super-resolution fluorescence microscopy studies performed in HeLa cells showed there was a high intracellular uptake of the chemosensor. Incubation in Cu2+ spiked media revealed a strong fluorescent signal from mitochondria and cell membranes, which is consistent with a high concentration of ATP at these intracellular sites.

Asunto(s)

RESUMEN

Several dinuclear terphenyl phosphine copper(I) halide complexes of composition [CuX(PR2Ar')]2 (X = Cl, Br, I; R = hydrocarbyl, Ar' = 2,6-diarylterphenyl radical), 1-5, have been isolated from the reaction of CuX with 1 equiv of the phosphine ligand. Most of them have been characterized by X-ray diffraction studies in the solid state, thus allowing comparative discussions of different structural parameters, namely, Cu···Cu and Cu···Aryl separations, conformations adopted by coordinated phosphines, and planarity of the Cu2X2 cores. Centrosymmetric complexes [CuI(PMe2ArXyl2)]2, 1c, and [CuI(PEt2ArMes2)]2, 3c, despite their similar structures, show very distinct photoluminescence (PL) in powder form at room temperature. The photophysical behavior of these compounds in liquid solution, solid-solid Zeonex solution and powder samples at room temperature and 77 K have been investigated and supported by DFT calculation. Identification of vibronic coupling modes, done by group theory calculations and the technique of projection operators, shows that the manifestation of these modes is conditioned by crystal packing. Complexes [CuI(PMe2ArXyl2)]2, 1c, and [CuI(PEt2ArMes2)]2, 3c, display remarkable activity in copper-catalyzed azide-alkyne cycloaddition reactions involving preformed and in situ-made azides. Reactions are performed in H2O, under aerobic conditions, with low catalyst loadings and tolerate the use of iodoalkynes as substrates.

RESUMEN

An unusual thermally sensitive anion-cation interaction, which is characteristic of the anion [Eu(FOD)4 ]- , occurs in the complex [CHOL][Eu(FOD)4 ] (1; CHOL=choline; FOD=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) and affects both quantum yield and thermochromic behavior. This prompted the design of an Eu3+ -based ratiometric thermometer that functions at temperatures up to 95 °C through a thermally excited state absorption of the Eu3+ ion. The reusable temperature-sensitive luminescent complex showed a range of relative sensitivity between 0.45 % C-1 at 25 °C, with an increase to 7.0 % C-1 at 95 °C. Confinement of compound 1 in a transparent film of polysulfone resulted in a higher thermal stability of 1 while its luminescence showed a strong temperature dependence.

RESUMEN

A new 2,7,10,15-tetraethynyldibenzo[g,p]chrysene ligand (1) and two tetranuclear gold(I) derivatives containing PPh3 (3) and PMe3 (4) phosphines were synthesized and characterized by 1H and 31P NMR, IR spectroscopy, and high-resolution mass spectrometry. The compounds were studied in order to analyze the effect of the introduction of gold(I) on the supramolecular aggregation and photophysical properties. Absorption and emission spectra displayed broad bands due to the establishment of π π interactions as an indication of intermolecular contacts and the formation of aggregates. A decrease of the recorded quantum yield (QY) of the gold(I) derivatives was observed compared to the uncomplexed ligand. The introduction of the complexes into poly methyl methacrylate (PMMA) and Zeonex 480R matrixes was analyzed, and an increase of the measured QY of 4 in Zeonex was observed. No phosphorescent emission was detected.

Asunto(s)

RESUMEN

An electronic spectral and photophysical characterization of three gold(I) complexes containing heterocyclic chromophores differing in the number and arrangement of pyridine rings (pyridine, bipyridine, and terpyridine, with the acronyms pD, bD, and tD respectively) was performed. Quantum yields of fluorescence, internal conversion and triplet state formation, together with the rate constants for singlet to triplet intersystem crossing, S1 ∼ ∼ ∼ S0 internal conversion and fluorescence were measured in order to equate the impact of fast triplet state formation on the amount of triplets formed. The results showed a correlation between the increase on the measured decay values of S1 (leading to the main formation of T1) and the increase in the charge transfer (CT) character of the lowest energy transition, as evaluated from the orthogonality of the frontier orbitals. The measured triplet state quantum yields range from ∼50-60% to 70%, whereas the intersystem crossing rate constants differ by almost 2 orders of magnitude, from 9.4 × 109 s-1 for tD to 8.1 × 1011 s-1 for bD. This constitutes an evidence for the existence of a correlation between the intersystem crossing and the internal conversion mechanisms.

RESUMEN

We report the first example of an observable and reversible case of thermochromism due to the interaction of an alkylphosphonium (P6,6,6,14)+ with a ß-diketonate (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate-fod) of an europium(iii) tetrakis-ß-diketonate room temperature ionic liquid. This thermochromism is characterized by the conversion of a light yellow viscous liquid, at room temperature, to a reddish substance close to 80 °C. The reversibility of this optical effect was highlighted by the thermal stability of the Eu(iii) complex.