Cyclometalated Au(III) complexes with alkynylphosphine oxide ligands: synthesis and photophysical properties.

A series of cyclometalated Au(III) complexes [Au(C^N^C)(C-L-P(O)Ph)] with C^N^C = 2,6-diphenylpyridine and alkynylphosphine oxide ligands (L = no linker, Au1; phenyl, Au2; biphenyl, Au3; naphthyl, Au4; anthracenyl, Au5) were synthesized and fully characterized by spectroscopic methods and single crystal XRD analysis. The complexes obtained exhibit triplet (Au1-Au3) and dual (Au4, Au5) emissions in solution, in the solid phase and in the PMMA film, whose characteristics depend on the linker's nature of the alkynylphosphine oxide ligand. The description of electronic transitions responsible for energy absorption and emission in Au(III) complexes was made on the basis of a detailed analysis of the results of DFT calculations and has shown to involve ILCT, LLCT and MLCT transitions of singlet and triplet nature.

Aggregation Game: Changing Solid-State Emission Using Different Counterions in Monoalkynylphosphonium Pt(II) Complexes.

Two series of heteroleptic monoalkynylphosphonium Pt(II) complexes decorated with 2,2':6',2''-terpyridine (, series) and 6-phenyl-2,2'-bipyridine (, series) ligands, were prepared and characterized by spectroscopic methods. The complexes obtained exhibit triplet emission in solution, and the characteristics inside the series depend on the nature of the alkynylphosphonium ligand. The description of electronic transitions responsible for energy absorption and emission in discrete Pt(II) complexes was made on the basis of a detailed analysis of the results of DFT calculations, and has shown to involve MLCT, ILCT, and LLCT transitions.

Cationic or Neutral: Dependence of Photophysical Properties of Bis-Alkynylphosphonium Pt(II) Complexes on Ancillary Ligand.

A series of D-π-A alkynylphosphonium salts with different linker between donor and acceptor groups was used to synthesize two series of trans-bis-alkynylphosphonium Pt(II) complexes with different ancillary ligands (triphenylphosphine, P series, and cyanide, CN series). The nature of the ancillary ligand manages the overall charge and emission properties of the complexes obtained. In addition, the variation of the linker in alkynylphosphonium ligands allows fine-tuning the luminescence wavelength.

Bioorthogonal chemistry of polyoxometalates - challenges and prospects.

Bioorthogonal chemistry has enabled scientists to carry out controlled chemical processes in high yields while minimizing hazardous effects. Its extension to the field of polyoxometalates (POMs) could open up new possibilities and new applications in molecular electronics, sensing and catalysis, including inside living cells. However, this comes with many challenges that need to be addressed to effectively implement and exploit bioorthogonal reactions in the chemistry of POMs.

Alkynylphosphonium Pt(II) Complexes: Synthesis, Characterization, and Features of Photophysical Properties in Solution and in the Solid State.

A series of heteroleptic bis-alkynyl-diimine mononuclear Pt(II) complexes with alkynylphosphonium and di--butyl-2,2'-bipyridine (dtbpy) ligands have been prepared and characterized by spectroscopic methods and single-crystal XRD. The Pt(II) complexes obtained in the present study demonstrate triplet emission in solution, which originates from MLCT/LC states where the nature of the π-conjugated linker in the alkynylphosphonium ligand manages the contributions of each transition, and this conclusion is supported by DFT calculations. Additionally, the presence of the phosphonium group connected to alkynyl through the π-conjugated linker enhances nonlinear optical properties of the Pt(II) complexes increasing two-photon absorption cross section up to 400 GM.

X/Y platinum(II) complexes: some features of supramolecular assembly halogen bonding.

Four series of new luminescent cyclometalated complexes [Pt(C^N)(IPy)Y] (HC^N = 2-phenylpyridine (Hppy), 2-(1-benzofuran-3-yl)pyridine (Hbfpy), methyl-2-phenylquinoline-4-carboxylate (Hmpqc), 2-(1-benzothiophen-3-yl)pyridine (Hbtpy), IPy = 4-iodopyridine, and Y = Cl, Br, I) have been investigated as X/Y 'building blocks' for the construction of a supramolecular network utilizing the I atom in IPy as a halogen bond (XB) donor (the X atom). The σ-hole of the X atom was found to provide non-covalent X⋯Y, X⋯Pt and X⋯π (π system of the metalated chelate ring) interactions for the complexes in the crystal state. NBO analysis confirms donation of the platinum electron density to iodine upon the X⋯Pt interaction.

Increasing the redox switching capacity of Lindqvist-type hexavanadates by organogold post-functionalisation.

The covalent attachment of organogold(I) moieties to the Lindqvist-type polyoxovanadate results in a measurable charge re-distribution across the formed Au-{V6}-Au linkages. Scanning probe microscopy studies of these hybrid compounds on the Au(111) surface demonstrate the increase in the number of switching states with stepwise increase in molecular conductance, compared with unfunctionalised hexavanadates.

No-Dose Photodynamic Therapy Against Half-Dose Photodynamic Therapy for Treatment of Central Serous Chorioretinopathy.

Introduction: This study aimed to describe the effects of no-dose full-fluence photodynamic therapy without verteporfin (no-dose PDT) and to compare no-dose PDT with half-dose verteporfin full-fluence photodynamic therapy (HDFF PDT) for managing chronic central serous chorioretinopathy (cCSC).

Methods: This retrospective study evaluated 11 patients with chronic recurrent CSC treated with no-dose PDT between January 2019 and March 2022. Most of these patients were also treated with HDFF PDT a minimum of 3 months before and were considered as the control group.

Homoleptic Alkynylpyridinium Au(I) Complexes as Organometallic 'D-π-A' Chromophores.

A series of terminal acetylenes bearing methylpyridinium acceptor group attached to the alkynyl unit with different π-conjugated aromatic linker have been synthetized. These alkynylpyridinium salts are efficient 'push-pull' chromophores demonstrating bright UV-vis fluorescence with quantum yields up to 70 %. The homoleptic bis-alkynyl Au(I) complexes based on these alkynylpyridinium ligands demonstrate complicated photophysical behavior including dual emission in solution.

Homoleptic Alkynylphosphonium Au(I) Complexes as Push-Pull Phosphorescent Emitters.

A series of compounds - bearing terminal alkynyl sites connected with a phosphonium group via different π-conjugated linkers have been synthesized. The compounds themselves are efficient push-pull emitters and exhibit bright fluorescence in blue and near-UV regions. - were used as alkynyl ligands to obtain a series of homoleptic bis-alkynyl Au(I) complexes -.

Post-Functionalization of Organometallic Complexes via Click-Reaction.

CuAAC (Cu catalyzed azide-alkyne cycloaddition) click-reaction is a simple and powerful method for the post-synthetic modification of organometallic complexes of transition metals. This approach allows the selective introduction of additional donor sites or functional groups to the periphery of the ligand environment. This is especially important if a metalloligand with free donor sites, which are of the same nature as the primary site for the coordination of the primary metal, has to be created.

So Close, Yet so Different: How One Donor Atom Changes Significantly the Photophysical Properties of Mononuclear Cu(I) Complexes.

The manipulation of the photophysical properties of molecular emitters can be realized by composing the close environment of the metal center with the "heavier pnictogen atom" effect. Replacing a nitrogen atom with a heavier phosphorus atom in otherwise isostructural molecular systems results in a significant change of the photophysical parameters. Herein, we report on the synthesis of four pairs of novel phosphinine-based and isostructural diimine-based Cu(I) complexes, which feature peculiar photophysical properties, and show how these parameters depend on the "heavier pnictogen atom" effect.

Controllable Synthesis and Luminescence Behavior of Tetrahedral Au@Cu and Au@Ag Clusters Supported by tris(2-Pyridyl)phosphine.

We report herein a family of polynuclear complexes, [Au@Ag(PyP)]X and [Au@Cu(PyP)]X [X = NO, ClO, OTf, BF, SbF], containing unprecedented Au-centered Ag and Cu tetrahedral cores supported by tris(2-pyridyl)phosphine (PyP) ligands. The [Au@Ag] clusters are synthesized controlled substitution of the central Ag(I) ion in all-silver [Ag@Ag] precursors by the reaction with Au()Cl, while the [Au@Cu] cluster is assembled through the treatment of a pre-organized [Au(PyP)] metallo-ligand with 4 equiv of a Cu(I) source. The structure of the Au@M clusters has been experimentally and theoretically investigated to reveal very weak intermolecular Au-M metallophilic interactions.

The Tail Wags the Dog: The Far Periphery of the Coordination Environment Manipulates the Photophysical Properties of Heteroleptic Cu(I) Complexes.

In this work we show, using the example of a series of [Cu(Xantphos)(N^N)] complexes (N^N being substituted 5-phenyl-bipyridine) with different peripheral N^N ligands, that substituents distant from the main action zone can have a significant effect on the physicochemical properties of the system. By using the C≡C bond on the periphery of the coordination environment, three hybrid molecular systems with -Si(CH), -Au(PR), and -CHN(CH)CH fragments were produced. The Cu(I) complexes thus obtained demonstrate complicated emission behaviour, which was investigated by spectroscopic, electrochemical, and computational methods in order to understand the mechanism of energy transfer.

Re(I) Complexes as Backbone Substituents and Cross-Linking Agents for Hybrid Luminescent Polysiloxanes and Silicone Rubbers.

This study focuses on the synthesis of hybrid luminescent polysiloxanes and silicone rubbers grafted by organometallic rhenium(I) complexes using Cu(I)-catalyzed azido-alkyne cycloaddition (CuAAC). The design of the rhenium(I) complexes includes using a diimine ligand to create an MLCT luminescent center and the introduction of a triple C≡C bond on the periphery of the ligand environment to provide click-reaction capability. Poly(3-azidopropylmethylsiloxane--dimethylsiloxane) (N-PDMS) was synthesized for incorporation of azide function in polysiloxane chain.

Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits.

A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππ stacking, CH-π, and CH-Au, but no aurophilic interactions are realized.

Functionalizing Collagen with Vessel-Penetrating Two-Photon Phosphorescence Probes: A New In Vivo Strategy to Map Oxygen Concentration in Tumor Microenvironment and Tissue Ischemia.

The encapsulation and/or surface modification can stabilize and protect the phosphorescence bio-probes but impede their intravenous delivery across biological barriers. Here, a new class of biocompatible rhenium (Re ) diimine carbonyl complexes is developed, which can efficaciously permeate normal vessel walls and then functionalize the extravascular collagen matrixes as in situ oxygen sensor. Without protective agents, Re -diimine complex already exhibits excellent emission yield (34%, λ   = 583 nm) and large two-photon absorption cross-sections (σ   = 300 GM @ 800 nm) in water (pH 7.

Keep it tight: a crucial role of bridging phosphine ligands in the design and optical properties of multinuclear coinage metal complexes.

Copper subgroup metal ions in the +1 oxidation state are classical candidates for aggregation via non-covalent metal-metal interactions, which are supported by a number of bridging ligands. The bridging phosphines, soft donors with a relatively labile coordination to coinage metals, serve as convenient and essential components of the ligand environment that allow for efficient self-assembly of discrete polynuclear aggregates. Simultaneously, accessible and rich modification of the organic spacer of such P-donors has been used to generate many fascinating structures with attractive photoluminescent behavior.

Hexavanadate-Organogold(I) Hybrid Compounds: Synthesis by the Azide-Alkyne Cycloaddition and Density Functional Theory Study of an Intriguing Electron Density Distribution.

The fully oxidized Lindqvist-type hexavanadate compounds decorated by phosphine-derivatized Au(I) moieties oriented in a fashion (-BuN)[VO{(OCH)CCH(NCCH)AuP(CHOMe)}] () and (-BuN)[VO{(OCH)CCHOCH(CNH)AuP(CHOMe)}] () have been prepared by azide-alkyne cycloaddition reactions and characterized by various techniques, including NMR, IR, and UV/vis spectroscopy and electrospray ionization mass spectrometry. Electronic structure calculations unveil the potential of these model hybrid junctions for application in controlled charge-transport experiments on substrate surfaces.

Modulation of Metallophilic and π-π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding.

Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC F as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1-3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1-3⋅⋅⋅IC F has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal-metal-to-ligand charge transfer) origin.

Silver-Decorated TiO Inverse Opal Structure for Visible Light-Induced Photocatalytic Degradation of Organic Pollutants and Hydrogen Evolution.

TiO inverse opal (TIO) structures were prepared by the conventional wet chemical method, resulting in well-formed structures for photocatalytic activity. The obtained structures were functionalized with liquid flame spray-deposited silver nanoparticles (AgNPs). The nanocomposites of TIO and AgNPs were extensively characterized by various spectroscopies such as UV, Raman, X-ray diffraction, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy combined with microscopic methods such as scanning electron microscopy, transmission electron microscopy (TEM), and high-resolution TEM.