Browse
Submit Data
Databases
API
Help

Dataset Information

26 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Dipyridylmethane Ethers as Ligands for Luminescent Ir Complexes.

ABSTRACT: This work reports two new cationic heteroleptic cyclometalated iridium complexes, containing ether derivatives of di(pyridin-2-yl)methanol. The new ligands are based on dipyridin-2-ylmethane and are designed to obtain ether-based intermediates with extended electronic conjugation by insertion of π system such as phenyl, allyl and ethynyl. Different synthetic strategies were employed to introduce these units, as molecular wires, between the dipyridin-2-ylmethane chelating portion and the terminal N-containing functional group, such as amine and carbamide. The corresponding complexes show luminescence in the blue region of the spectrum, lifetimes between 0.6 and 2.1 μs, high quantum yield and good electrochemical behavior. The computational description (DFT) of the electronic structure highlights the key role of the conjugated π systems on optical and electrochemical properties of the final products.

SUBMITTER: Volpi G

PROVIDER: S-EPMC8659258 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Luminescent Metal Complexes Featuring Photophysically Innocent Boron Cluster Ligands.

Project description:We report the synthesis and characterization of a series of d8 metal complexes featuring robust and photophysically innocent strong-field chelating 1,1'-bis(o-carborane) (bc) ligand frameworks. A combination of UV-Vis spectroscopy, single crystal X-ray structural analysis, and DFT calculations of these species suggest that the dianionic bc ligand does not contribute to any visible metal-to-ligand charge transfer (MLCT) transitions, yet it provides a strong ligand field in these complexes. Furthermore, a bc-based Pt(II) complex containing a 4,4'-di-tert-butyl-2,2'-bipyridine ligand (dtb-bpy) has been prepared and was found to display blue phosphorescent emission dominated by MLCT from the Pt(II) center to the dtb-bpy ligand. Importantly, the bulky three-dimensional nature of the bc ligand precludes intermolecular Pt(II)⋯Pt(II) interactions in the solid state where the resulting compounds retain their emission properties. This study opens a potentially new avenue for designing organic light-emitting diode (OLED) materials with tunable properties featuring photophysically innocent boron-rich cluster ligands.

| S-EPMC5300762 | biostudies-literature

Series of Near-IR-Absorbing Transition Metal Complexes with Redox Active Ligands.

Project description:New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N'-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications.

| S-EPMC7321360 | biostudies-literature

Liquid Crystalline and Gel Properties of Luminescent Cyclometalated Palladium Complexes with Benzoylthiourea Ligands.

Project description:The design and development of new luminescent metallogels formed by cyclometalated palladium(II) complexes in protic solvents were investigated by a combination of differential scanning calorimetry (DSC), polarized optical microscopy (POM), and rheology. Cyclometalated palladium(II) complexes based on imine ligand and ancillary benzoylthiourea (BTU) ligand showed red emission in solid and gel states. The formation of a lyotropic liquid crystal phase was observed for the complex bearing shorter alkyl groups on the BTU ligand. This complex also behaved as a thermotropic liquid crystal that displays a monotropic smectic A phase (SmA). Dynamic rheology measurements (frequency sweep in the 5-90 °C range) of the 1-decanol solution of palladium(II) complexes highlighted their supramolecular self-association ability to generate 3D networks and form gels as a final result.

| S-EPMC10606689 | biostudies-literature

Azo-triazolide bis-cyclometalated Ir(iii) complexes via cyclization of 3-cyanodiarylformazanate ligands.

Project description:In this work we describe the synthesis of sterically encumbered 1,5-diaryl-3-cyanoformazanate bis-cyclometalated iridium(iii) complexes, two of which undergo redox-neutral cyclization during the reaction to produce carbon-bound 2-aryl-4-arylazo-2H-1,2,3-triazolide ligands. This transformation offers a method for accessing 2-aryl-4-arylazo-2H-1,2,3-triazolide ligands, a heretofore unreported class of chelating ligands. One formazanate complex and both triazolide complexes are structurally characterized by single-crystal X-ray diffraction, with infrared spectroscopy being the primary bulk technique to distinguish the formazanate and triazolide structures. All complexes are further characterized by UV-Vis absorption spectroscopy and cyclic voltammetry, with the triazolide compounds having similar frontier orbital energies to the formazanate complexes but much less visible absorption.

| S-EPMC7328346 | biostudies-literature

Luminescent properties of ruthenium(II) complexes with sterically expansive ligands bound to DNA defects.

Project description:A new family of ruthenium(II) complexes with sterically expansive ligands for targeting DNA defects was prepared, and their luminescent responses to base pair mismatches and/or abasic sites were investigated. Design of the complexes sought to combine the mismatch specificity of sterically expansive metalloinsertors, such as [Rh(bpy)2(chrysi)](3+) (chrysi = chrysene-5,6-quinone diimine), and the light switch behavior of [Ru(bpy)2(dppz)](2+) (dppz = dipyrido[3,2-a:2',3'-c]phenazine). In one approach, complexes bearing analogues of chrysi incorporating hydrogen-bonding functionality similar to dppz were synthesized. While the complexes show luminescence only at low temperatures (77 K), competition experiments with [Ru(bpy)2(dppz)](2+) at ambient temperatures reveal that the chrysi derivatives preferentially bind DNA mismatches. In another approach, various substituents were introduced onto the dppz ligand to increase its steric bulk for mismatch binding while maintaining planarity. Steady state luminescence and luminescence lifetime measurements reveal that these dppz derivative complexes behave as DNA "light switches" but that the selectivity in binding and luminescence with mismatched/abasic versus well-matched DNA is not high. In all cases, luminescence depends sensitively upon structural perturbations to the dppz ligand.

| S-EPMC3622160 | biostudies-literature

Theoretical Approach for the Luminescent Properties of Ir(III) Complexes to Produce Red-Green-Blue LEC Devices.

Project description:With an appropriate mixture of cyclometalating and ancillary ligands, based on simple structures (commercial or easily synthesized), it has been possible to design a family of eight new Ir(III) complexes (1A, 1B, 2B, 2C, 3B, 3C, 3D and 3E) useful as luminescent materials in LEC devices. These complexes involved the use of phenylpyridines or fluorophenylpyridines as cyclometalating ligands and bipyridine or phenanthroline-type structures as ancillary ligands. The emitting properties have been evaluated from a theoretical approach through Density Functional Theory and Time-Dependent Density Functional Theory calculations, determining geometric parameters, frontier orbital energies, absorption and emission energies, injection and transport parameters of holes and electrons, and parameters associated with the radiative and non-radiative decays. With these complexes it was possible to obtain a wide range of emission colours, from deep red to blue (701-440 nm). Considering all the calculated parameters between all the complexes, it was identified that 1B was the best red, 2B was the best green, and 3D was the best blue emitter. Thus, with the mixture of these complexes, a dual host-guest system with 3D-1B and an RGB (red-green-blue) system with 3D-2B-1B are proposed, to produce white LECs.

| S-EPMC9104581 | biostudies-literature

Molecular Design of Luminescent Complexes of Eu(III): What Can We Learn from the Ligands.

Project description:The luminescent metal-organic complexes of rare earth metals are advanced materials with wide application potential in chemistry, biology, and medicine. The luminescence of these materials is due to a rare photophysical phenomenon called antenna effect, in which the excited ligand transmits its energy to the emitting levels of the metal. However, despite the attractive photophysical properties and the intriguing from a fundamental point of view antenna effect, the theoretical molecular design of new luminescent metal-organic complexes of rare earth metals is relatively limited. Our computational study aims to contribute in this direction, and we model the excited state properties of four new phenanthroline-based complexes of Eu(III) using the TD-DFT/TDA approach. The general formula of the complexes is EuL2A3, where L is a phenanthroline with -2-CH3O-C6H4, -2-HO-C6H4, -C6H5 or -O-C6H5 substituent at position 2 and A is Cl- or NO3-. The antenna effect in all newly proposed complexes is estimated as viable and is expected to possess luminescent properties. The relationship between the electronic properties of the isolated ligands and the luminescent properties of the complexes is explored in detail. Qualitative and quantitative models are derived to interpret the ligand-to-complex relation, and the results are benchmarked with respect to available experimental data. Based on the derived model and common molecular design criteria for efficient antenna ligands, we choose phenanthroline with -O-C6H5 substituent to perform complexation with Eu(III) in the presence of NO3¯. Experimental results for the newly synthesized Eu(III) complex are reported with a luminescent quantum yield of about 24% in acetonitrile. The study demonstrates the potential of low-cost computational models for discovering metal-organic luminescent materials.

| S-EPMC10221419 | biostudies-literature

Synthesis and Spectroscopic and Luminescent Properties of Er, Yb and Lu Complexes with Cyano-Substituted Phthalocyanine Ligands.

Project description:Based on 4,4'-[1,3/4-phenilenebis(oxy)]phthalodinitriles, the mixture of phthalocyaninates of various structures with rare-earth metals were obtained by template fusion method minimizing the side polymerization processes. Target monophthalocyaninates were isolated from the reaction mixture and purified using column and then gel permeation chromatography. The compounds were characterized by NMR, IR spectroscopy, mass spectrometry, and elemental analysis. The spectral properties were studied and the aggregation behavior of the synthesized Er, Yb, and Lu phthalocyaninates in chloroform, acetone, and tetrahydrofuran was determined. It has been shown that lutetium complexes with 3,4-dicyanophenoxyphenoxy ligands are the least stable and least resistant to aggregation in solution, while erbium and ytterbium phthalocyaninates proved to be stable in all studied media. The quantum yields and fluorescence lifetimes of the complexes in chloroform and tetrahydrofuran were calculated.

| S-EPMC9267990 | biostudies-literature

Colorimetry of Luminescent Lanthanide Complexes.

Project description:Europium, terbium, dysprosium, and samarium are the main trivalent lanthanide ions emitting in the visible spectrum. In this work, the potential of these ions for colorimetric applications and colour reproduction was studied. The conversion of spectral data to colour coordinates was undertaken for three sets of Ln complexes composed of different ligands. We showed that Eu is the most sensitive of the visible Ln ions, regarding ligand-induced colour shifts, due to its hypersensitive transition. Further investigation on the spectral bandwidth of the emission detector, on the wavelengths' accuracy, on the instrumental correction function, and on the use of incorrect intensity units confirm that the instrumental correction function is the most important spectrophotometric parameter to take into account in order to produce accurate colour values. Finally, we established and discussed the entire colour range (gamut) that can be generated by combining a red-emitting Eu complex with a green-emitting Tb complex and a blue fluorescent compound. The importance of choosing a proper white point is demonstrated. The potential of using different sets of complexes with different spectral fingerprints in order to obtain metameric colours suitable for anti-counterfeiting is also highlighted. This work answers many questions that could arise during a colorimetric analysis of luminescent probes.

| S-EPMC7570272 | biostudies-literature

Synthesis of New Donor-Substituted Biphenyls: Pre-ligands for Highly Luminescent (C^C^D) Gold(III) Pincer Complexes.

Project description:We herein report on new synthetic strategies for the preparation of pyridine and imidazole substituted 2,2'-dihalo biphenyls. These structures are pre-ligands suitable for the preparation of respective stannoles. The latter can successfully be transmetalated to K[AuCl4 ] forming non-palindromic [(C^C^D)AuIII ] pincer complexes featuring a lateral pyridine (D=N) or N-heterocyclic carbene (NHC, D=C') donor. The latter is the first report on a pincer complex with two formally anionic sp2 and one carbenic carbon donor. The [(C^C^D)AuIII ] complexes show intense phosphorescence in solution at room temperature. We discuss the developed multistep strategy and touch upon synthetic challenges. The prepared complexes have been fully characterized including X-ray diffraction analysis. The gold(III) complexes' photophysical properties have been investigated by absorption and emission spectroscopy as well as quantum chemical calculations on the quasi-relativistic two-component TD-DFT and GW/Bethe-Salpeter level including spin-orbit coupling. Thus, we shed light on the electronic influence of the non-palindromic pincer ligand and reveal non-radiative relaxation pathways of the different ligands employed.

| S-EPMC7821303 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data