Steady-state irradiation under visible light of a covalent Ir(III)-photosensitized polyoxotungstate is reported. In the presence sacrificial electron donor, photolysis leads to very efficient photoreduction polyoxometalate. Successive formation one-electron and two-electron reduced species, which are unambiguously identified by comparison with spectroelectrochemical measurements, observed significantly faster rate reaction for species. The kinetics photoreduction, correlated reduction...

Abstract Enantioenriched bicyclo[4.1.0]hept‐2‐enes were synthesized by Ir I ‐catalyzed carbocyclization of 1,6‐enynes. No chiral ligands used, CO and PPh 3 the only bound to iridium. Instead, stereochemical information was localized on counterion catalyst, generated in situ reaction Vaska’s complex ( trans ‐[IrCl(CO)(PPh ) 2 ]) with a silver phosphate. Enantiomeric excesses up 93 % obtained when this catalytic mixture used. 31 P NMR IR spectroscopy suggest that formation ‐ [Ir(CO)(PPh ] +...

Keggin and Dawson-type polyoxometalates (POMs) covalently grafted to heteroleptic cyclometalated iridium(III) complexes (POM–[Ir] dyads) have been prepared by postfunctionalization of organosilyl organotin POM derivatives. Electronic properties these 4 photosensitized POM–[Ir] dyads were evaluated electrochemical measurements theoretical calculations. These studies reveal that the electron acceptor character POMs vary with structural class (Keggin vs. Dawson) chemical anchorage (organosilyl...

Self-assembly of coordination frameworks exhibiting original architectures is an active area research. Generally, such assemblies are constructed from organic spacers and transition metals different geometrical structures. Herein, we report a novel class supramolecular with organometallic linkers based on metalated quinonoid thioquinonoid complexes that serve as spacers. The ligands stable have the general formula [Cp*M(eta(4)-benzoquinone)] (o- p-benzoquinone, Cp*=C(5)Me(5), M=Rh, Ir)...

Caught in the act: The first stable η4-diseleno-p-benzoquinone complex, [Cp*Ir(η4-C6H4Se2)], has been isolated. X-ray structure (see picture; Ir magenta, Se yellow) confirms coordination of elusive diselenobenzoquinone intermediate. anticancer activity this complex was compared to related oxygen and sulfur analogues; only diseleno cytotoxic, having a comparable cisplatin.

A novel heteroleptic cyclometalated iridium(III) complex with one picolinic acid derivative bearing a pendant terminal alkynyl tether has been prepared following new synthetic route. This can be further engaged in palladium C–C coupling reactions, allowing its grafting to Keggin-type polyoxometalate and thus providing unique iridio-POM conjugate.

Unlike p-dithiobenzoquinone (), which is extremely reactive and has never been isolated, the metal-stabilised [Cp*Ir(eta4-C6H4S2)] () was prepared used as an efficient organometallic linker to construct novel supramolecular assemblies. Treatment of with electrophilic Pt(II)(terpy) building blocks produced assembly {[Pt(terpy){Cp*Ir-p-(eta4-C6H4S2)}Pt(terpy)][OTf]4}n fully characterised its molecular structure determined by X-ray crystallography. The revealed presence pi-pi Pt[dot dot dot]Pt...

The first luminescent cyclometallated platinum(II) complex bearing phosphinine co-ligands is reported. long-lived luminescence, which it displays at 77 K, assigned to a phosphinine-localised triplet excited state on the basis of electrochemical data and TD-DFT calculations.

Enantioselective cationic Rh(I)-catalyzed [2+2+2] cycloaddition reactions between diynes and isocyanates relying on the chiral anion strategy have been devised. In presence of [Rh(cod)Cl]2, 1,4-bis(diphenylphosphino)butane, silver phosphate salt Ag(S)-TRIP as unique source chirality, axially pyridones were isolated with ees up to 82%. This approach is novel in field anion-mediated asymmetric catalysis since atroposelective transformations so far remained unprecedented. It also proves be...

Treatment of hydroquinone with [Cp*M(solvent)3][OTf]2 (M = Rh, Ir) in acetone afforded the π-bonded complexes {[Cp*M(η5-semiquinone)][OTf]}n Rh (1a), M Ir (1b)) 95% yield. The 1H NMR spectra 1a,b recorded CD3OD indicate strong hydrogen bonding solution. crystal structures 1a and 1b were determined exhibit intermolecular bonding, forming organometallic polymers which integrity system is maintained by between metal−semiquinone subunits. Deprotonation produced related η4-quinone complex...

We report the synthesis of π-bonded ruthenium, rhodium, and iridium o-benzoquinones [Cp*M(o-C6H4O2)]n [M = Ru (2), n 1–; Rh (3), 0; Ir (4), 0] following a novel synthetic procedure. Compounds 2–4 were fully characterized by spectroscopic methods used as chelating organometallic linkers, "OM-linkers", toward luminophore bricks such Ru(bpy)22+, Rh(ppy)2+, Ir(ppy)2+ (bpy 2,2′-bipyridine; ppy 2-phenylpyridine) for design family octahedral bimetallic complexes general formula...

We report the first synthesis of π-bonded rhodio and iridio-o-benzoquinones [Cp*M(o-benzoquinone)] (M = Rh (3a); M Ir (3b)) following a novel synthetic procedure. These compounds were fully characterized by spectroscopic methods; in particular X-ray molecular structure 3b was determined. Compounds 3a,b used as chelating organometallic linkers for design new family chiral octahedral bimetallic complexes, 4−9. The [(bpy)2Ru(3b)][OTf]2 (5) is presented shows that linker ruthenium center. In...

A series of bipyridyl (bpy) Pt(II) complexes with π-bonded catecholate (cat) [(bpy)Pt(LM)][BF4]n (2–5) (LM = Cp*Rh(cat), n 2; Cp*Ir(cat), Cp*Ru(cat), 1; and (C6H6)Ru(cat), 2) were prepared fully characterized. The molecular structures the four compounds determined showed that solid-state packing is different dependent on unit. For instance, while (bpy)Pt(II) 2 3 rhodium iridium catecholates did not show any Pt···Pt interactions those ruthenium 4 5 presence π–π among individual units...

Mechanochromic phosphorescence of a rare copper( i ) dinuclear complex with an extremely short Cu( )⋯Cu( separation.

Overcoming a long-standing challenge: A rational synthetic procedure allows the isolation of first stable η4-dithio-para-benzoquinone complex (2; Cp*=C5Me5). The X-ray molecular structure 2 confirms coordination elusive intermediate 1 in an η4 manner. Computational analyses support role {Cp*Ir} fragment stabilizing this reactive intermediate.

We report the use of organometallic linker [Cp*Ir(η4-benzoquinone)] (1b) LIr to construct novel supramolecular one- and two-dimensional (1D 2D) coordination polymers {[Cu2(LIr)2(CH3CN)(OTf)2][LIr](OTf)}n (3) {[Ag2(CH3CN)2][LIr]2(OTf)2}n (4). Complex 3 formed a zigzag chain Cu(I) Cu(II) centers connected through irido-quinonoid backbones, while complex 4 exhibited argentopilic Ag---Ag d10---d10 contacts at d = 3.638 Å C---H/π interactions between 1D neighbors.

Abstract Overcoming a long‐standing challenge, the o ‐ and p ‐dithiobenzoquinone iridium complexes [Cp*Ir‐ ‐(η 4 ‐C 6 H S 2 )] ( ) 7 were rationally synthesized fully characterized for first time including X‐ray molecular structure of ). Our strategic approach involves preparation halogenated 1,2‐ 1,4‐dichloro arene π Cl )][BF ] 5 ), which are key molecules . Subsequent treatment with NaSH halogen displacement provides target thioquinonoid in 88 % 95 yields respectively. Further,...

Abstract The chiral octahedral bimetallic assemblies [(bpy) 2 Ru( o ‐ L Ir )][CF 3 SO ] (2), [(ppy) Rh( )][NO (7) and Ir( (8) featuring chelating organometallic linker [Cp*Ir(η 4 o‐ benzoquinone)] ( ) have been prepared fully characterized. Anion metathesis following a convenient procedure allowed the preparation of related diastereomers [Δ‐(bpy) )][Δ‐TRISPHAT] 2a [Λ‐(bpy) 2b as well rhodium [(Δ, Λ)‐(ppy) 7a , 7b iridium 8a 8b assemblies. 1 H NMR studies in solution carried out on these...

We report the synthesis of a unique class luminescent heterotrinuclear complexes general formulas [Pt(terpy){Cp*Ir-p-(η4-C6H4Se2)}Pt(terpy)][X]4 (X = OTf, 3a; PF6, 3b; BF4, 3c; ClO4, 3d; BPh4, 3e). In these coordination assemblies two Pt(terpy) moieties are held by stable η4-diseleno-p-benzoquinone complex [Cp*Ir-p-(η4-C6H4Se2)]. The molecular structures solvates 3a and 3b were ascertained single-crystal X-ray diffraction study confirmed formation target molecules. solid-state packing...

We report the synthesis and luminescence properties of a novel platinum(<sc>ii</sc>)–silver(<sc>i</sc>) cluster exhibiting supramolecular donor–acceptor dative Pt → Ag bonds as well d¹⁰⋯d¹⁰ argentophilic interactions.

Photoluminescent pincer-like Pd(<sc>ii</sc>) and Pt(<sc>ii</sc>) complexes with a rare tridentate N^C^N ligand six membered NHC central core are described. Solid-state packing exhibits M(<sc>ii</sc>)⋯M(<sc>ii</sc>) π–π interactions.

A series of cyclometalated platinum(II) complexes the type [(ppy)Pt(LM)]n+ (n = 0, 1) with π-bonded catecholates acting as organometallic ligands (LM) have been prepared and characterized by analytical techniques. In addition, structures two were determined single-crystal X-ray diffraction. The packing shows formation a 1D supramolecular assembly generated dPt–πCp* interactions among individual units. All are luminescent in solid state solution media. results photophysics rationalized means...

Abstract Two cycloplatinated complexes of the form [Pt(NC)CH 3 ( P )] + incorporating a rare, bidentate NC‐chelating pyridylpyridylidene ligand are reported. The phosphorus‐based is either 2,4,6‐triphenylphosphinine or triphenylphosphine. These mononuclear have been fully characterised in solution and by single‐crystal X‐ray diffraction analysis. UV/Vis absorption photoluminescence spectroscopy studies reveal strong phosphorescence from phosphinine compound at 77 K but no emission its...