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Synthesis and photophysical properties of linear gold(I) complexes based on a CCC carbene.

ABSTRACT: The reaction between allenylpyridine (L1) and (Me₂S)AuCl resulted in the quantitative formation of the (Indolizy)gold chloride complex 1 (Indolizy = indolizin-2-ylidene). The reaction of 1 with carbazole in the presence of KO^tBu affords the corresponding (Indolizy)Au(Cz) complex 2. Both compounds show high air- and temperature stability. The crystal structure of 2 confirmed the linear co-planar geometry. Complex 1 shows an intense low energy absorption of mixed character in the UV-vis spectrum, ascribed to intraligand and (M + Hal)L charge transfer processes, and exhibits bright yellow phosphorescence with an excited state lifetime of 62.8 μs in the crystal and a luminescence quantum yield up to 65%. On the other hand, the carbazolate complex 2 in a polystyrene matrix shows bright red delayed fluorescence at 617 nm with a sub-microsecond excited state lifetime and a quantum yield of 21.6%.

SUBMITTER: Romanov AS

PROVIDER: S-EPMC8631002 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Gold Nanoclusters: Bridging Gold Complexes and Plasmonic Nanoparticles in Photophysical Properties.

Project description:Recent advances in the determination of crystal structures and studies of optical properties of gold nanoclusters in the size range from tens to hundreds of gold atoms have started to reveal the grand evolution from gold complexes to nanoclusters and further to plasmonic nanoparticles. However, a detailed comparison of their photophysical properties is still lacking. Here, we compared the excited state behaviors of gold complexes, nanolcusters, and plasmonic nanoparticles, as well as small organic molecules by choosing four typical examples including the Au10 complex, Au25 nanocluster (1 nm metal core), 13 diameter Au nanoparticles, and Rhodamine B. To compare their photophysical behaviors, we performed steady-state absorption, photoluminescence, and femtosecond transient absorption spectroscopic measurements. It was found that gold nanoclusters behave somewhat like small molecules, showing both rapid internal conversion (<1 ps) and long-lived excited state lifetime (about 100 ns). Unlike the nanocluster form in which metal-metal transitions dominate, gold complexes showed significant charge transfer between metal atoms and surface ligands. Plasmonic gold nanoparticles, on the other hand, had electrons being heated and cooled (~100 ps time scale) after photo-excitation, and the relaxation was dominated by electron-electron scattering, electron-phonon coupling, and energy dissipation. In both nanoclusters and plasmonic nanoparticles, one can observe coherent oscillations of the metal core, but with different fundamental origins. Overall, this work provides some benchmarking features for organic dye molecules, organometallic complexes, metal nanoclusters, and plasmonic nanoparticles.

| S-EPMC6669669 | biostudies-literature

Synthesis, Structures, and Photophysical Properties of Novel Four-Coordinate Cu(I) Complexes Supported by Chelating N-Heterocyclic Carbene Ligands.

Project description:Luminescent Cu(I) complexes are promising emitting materials for electroluminescent devices due to their low cost and abundant resources, as well as high emission efficiency. It is well-known that N-heterocyclic carbenes (NHCs) are excellent ligands for transition metal complexes. To investigate the photophysical properties of Cu(I)-NHC complexes, a series of new mononuclear four-coordinate Cu(I) complexes supported by the diphosphine ligand bis[2-(diphenylphosphino)phenyl]ether (POP) and the NHC ligands, consisting of imidazolylidene and pyrimidine units, were synthesized and fully characterized. To tune the photophysical properties of these Cu(I)-NHC complexes, the NHC ligands were attached with electron-withdrawing/donating groups (fluorine, chlorine, methyl and methoxyl) at the pyrimidine unit. All of these Cu(I)-NHC complexes adopt the typical distorted tetrahedral configuration. The electron-donating groups can lead to shorter Cu-N bond distances and longer Cu-C bond distances compared to the electron-withdrawing groups. Theoretical calculation results show that the highest occupied molecular orbitals are mainly distributed on the Cu(I) ion, POP, and carbene unit, while the lowest unoccupied molecular orbitals are mostly located on the pyrimidine unit of NHC ligands. The lowest energy electronic transitions of these Cu(I)-NHC complexes are mainly the metal-to-ligand charge transfer transition and ligand-to-ligand charge transfer transition. These Cu(I)-NHC complexes in solid state show tunable emissions from 530 to 618 nm with efficiencies of 0.5-38.1% at room temperature. The photophysical behaviors of these complexes at 298 and 50 K match well with the thermally activated delayed fluorescence (TADF) characteristics.

| S-EPMC6561309 | biostudies-literature

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Project description:The golden state: selective 5-exo- and 6-endo-cyclizations of an alkynyl benzothioamide have been achieved. The selectivity is controlled by the oxidation state of the gold precursor (+I or +III), yielding two new types of carbene ligand: an (aryl)(heteroaryl)carbene and a six-membered mesoionic carbene. Mes=2,4,6-trimethylphenyl.

| S-EPMC3712865 | biostudies-literature

Synthesis and Photophysical Properties of T-Shaped Coinage-Metal Complexes.

Project description:The photophysical properties of a series of T-shaped coinage d10 metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T-shaped AgI complex. Post-complexation modification of the AuI complex provides access to a linear cationic AuI complex following ligand alkylation, or the first example of a cationic square planar AuIII -F complex from electrophilic attack on the metal centre. Emissions ranging from blue (CuI ) to orange (AgI ) are obtained, with variable contributions of thermally-dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T-shaped AuI , cationic linear AuI and square planar cationic AuIII ). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution.

| S-EPMC7317956 | biostudies-literature

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Project description:The stereoselective synthesis of a highly luminescent neutral Ir(III) complex comprising two bidentate chiral, cyclometalating phenylpyridine derivatives, and one acetylacetonate as ligands is described. The final complex and some intermediates were characterized by X-ray structural analysis, NMR-, CD-, and CPL-spectroscopy.

| S-EPMC2711639 | biostudies-literature

Towards Iron(II) Complexes with Octahedral Geometry: Synthesis, Structure and Photophysical Properties.

Project description:The control of ligand-field splitting in iron (II) complexes is critical to slow down the metal-to-ligand charge transfer (MLCT)-excited states deactivation pathways. The gap between the metal-centered states is maximal when the coordination sphere of the complex approaches an ideal octahedral geometry. Two new iron(II) complexes (C1 and C2), prepared from pyridylNHC and pyridylquinoline type ligands, respectively, have a near-perfect octahedral coordination of the metal. The photophysics of the complexes have been further investigated by means of ultrafast spectroscopy and TD-DFT modeling. For C1, it is shown that-despite the geometrical improvement-the excited state deactivation is faster than for the parent pseudo-octahedral C0 complex. This unexpected result is due to the increased ligand flexibility in C1 that lowers the energetic barrier for the relaxation of 3MLCT into the 3MC state. For C2, the effect of the increased ligand field is not strong enough to close the prominent deactivation channel into the metal-centered quintet state, as for other Fe-polypyridine complexes.

| S-EPMC7767130 | biostudies-literature

Ionization of gold (γ-methoxy)vinyl complexes generates reactive gold vinyl carbene complexes.

Project description:Cationic gold vinyl carbene/allylic cation complexes of the form (E)-[(L)AuC(H)C(H)CAr2]+ OTf- {L = IPr, Ar = Ph [(E)-5a], L = IPr, Ar = 4-C6H4OMe [(E)-5b], L = P(t-Bu)2 o-biphenyl, Ar = 4-C6H4OMe [(E)-5c]} were generated in solution via Lewis acid-mediated ionization of the corresponding gold (γ-methoxy)vinyl complexes (E)-(L)AuC(H)C(H)C(OMe)Ar2 at or below -95 °C. Complexes (E)-5b and (E)-5c were fully characterized in solution employing multinuclear NMR spectroscopy, which established the predominant contribution of the aurated allylic cation resonance structure and the significant distribution of positive charge into the γ-anisyl rings. Complex (E)-5b reacted rapidly at -95 °C with neutral two-electron, hydride, and oxygen atom donors exclusively at the C1 position of the vinyl carbene moiety and with p-methoxystyrene to form the corresponding vinylcyclopropane. In the absence of nucleophile (E)-5a decomposed predominantly via intermolecular carbene dimerization whereas formation of 1-aryl-5-methoxy indene upon ionization of (Z)-(IPr)AuC(H)C(H)C(OMe)(4-C6H4OMe)2 [(Z)-6b] implicated an intramolecular Friedel-Crafts or electrocyclic Nazarov pathway for the decomposition of the unobserved vinyl carbene complex (Z)-[(IPr)AuC(H)C(H)C(4-C6H4OMe)2]+ OTf- [(Z)-5b].

| S-EPMC6585879 | biostudies-literature

A bonding model for gold(I) carbene complexes.

Project description:The last decade has witnessed dramatic growth in the number of reactions catalyzed by electrophilic gold complexes. While proposed mechanisms often invoke the intermediacy of gold-stabilized cationic species, the nature of bonding in these intermediates remains unclear. Herein, we propose that the carbon-gold bond in these intermediates is comprised of varying degrees of both sigma and pi-bonding; however, the overall bond order is generally less than or equal to unity. The bonding in a given gold-stabilized intermediate, and the position of this intermediate on a continuum ranging from gold-stabilized singlet carbene to gold-coordinated carbocation, is dictated by the carbene substituents and the ancillary ligand. Experiments show that the correlation between bonding and reactivity is reflected in the yield of gold-catalyzed cyclopropanation reactions.

| S-EPMC2748951 | biostudies-literature

Cobaltoceniumselenolate Gold(I) Complexes: Synthesis, Spectroscopic, Structural and Anticancer Properties.

Project description:Cobaltoceniumselenolate is an unusual, highly air-sensitive, mesoionic compound containing a very soft anionic selenium donor atom. Here we explore its coordination chemistry with Au(I) metal centers and show that its hetero- and homoleptic gold complexes are highly colored, air-stable compounds, which were characterized by 1H/13C/31P/77Se NMR, IR, UV-Vis, HR-MS and single crystal XRD. Cytotoxicity of these polar, water-soluble complexes was studied against various standard cancer cell lines (A549MDA-MB-231, HT-29) revealing good anticancer activity of all three complexes.

| S-EPMC8362036 | biostudies-literature

Synthesis and Emergent Photophysical Properties of Diketopyrrolopyrrole-Based Supramolecular Self-Assembly.

Project description:Diketopyrrolopyrrole (DPP)-based molecular semiconductors exhibit intriguing optical and charge transport properties. Herein, we rationally design a series of electronically identical but structurally distinct Hamilton receptor (HR)-based supramolecular assembly of DPP. The HR endows supramolecular assemblies via hydrogen bonding with enhanced structural ordering and excitonic couplings. The mechanism of supramolecular self-assembly was probed by diffusion ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) and solid-state IR spectroscopy studies. We investigated the morphology of self-assembly, photophysical and electrochemical properties and compared them with the identical DPP molecular structures without HRs. The microstructure of self-assembly was probed with atomic force microscopy in thin films. Subsequently, the influence of solid-state packing was studied by single-crystal X-ray diffraction. The single-crystal structure of HR-TDPP-C20 reveals slipped stack arrangements between the two neighboring chromophores with π-π stacking distance and slip angle of 3.55 Å and 35.4°, respectively. Notably, the slight torsional angle of 1° between thiophene and lactam rings and small π-π stacking distance suggest a significant intermolecular coupling between thiophene (D) and lactam (A) rings. This intramolecular coupling between two π-π chromophore stacks manifests in their optical properties. In this manuscript, we report rational design and synthesis of supramolecular self-assembly of DPP with a collection of compelling structural and optical properties.

| S-EPMC9280760 | biostudies-literature

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