-M(CO)(PNP) pincer complexes (M = W(0) or Re(I); PNP = 4,5-bis(diphenylphosphino)acridine): synthesis, spectroscopy and anti-Kasha emission.

Two isoelectronic and isostructural W(0) and Re(I) complexes -W(CO)(PNP) (1) and [-Re(CO)(PNP)]Cl (2) (PNP = 4,5-bis(diphenylphosphino)acridine) were synthesized and characterized by X-ray diffraction, infrared, electronic absorption and emission spectroscopy, and cyclic voltammetry. Structures of these complexes show a metal center bonded to the pincer ligand and two axial CO and one equatorial CO ligands. DFT calculations showed that the LUMOs of both complexes are the lowest energy π* orbitals localized in the acridine part of the ligand.

Pristine cobalt humic acid xerogels embedded with ultrafine cobalt sulfide for enhanced and stable lithium-ion storage.

The electrochemical performance of pristine metal-organic xerogels as anodes in lithium-ion batteries is reported for the first time. We propose a novel synthesis approach for the in situ generation of highly dispersed, ultrafine cobalt sulfide nanoparticles on humic acid gels (CoSHA). The CoS nanoparticles in CoSHA have an average diameter of approximately 3 nm.

Hetero- and homoleptic binuclear gold(I)-thiolate and -halide complexes - ligand exchange kinetics and supramolecular structures.

Heteroleptic and homoleptic binuclear Au(I) complexes [Au2(μ-PAnP)(SPh)(X)] (X = Cl or Br), [Au2(μ-PAnP)(SPh)2] and [Au2(μ-PAnP)(SPhCO2H)2] (SPh = benzenethiolate and SPhCOH = 4-thiolatobenzoic acid) containing the bridging diphosphine, 9,10-bis(diphenylphosphino)anthracene (PAnP), were synthesized and characterized by single crystal X-ray diffraction. [Au2(μ-PAnP)(SPh)2] exists as a monomer in its crystals but [Au2(μ-PAnP)(SPhCO2H)2] polymerizes into zig-zag chains intermolecular hydrogen bonding. [Au2(μ-PAnP)(SPh)(Cl)] forms cyclophane-like dimers of symmetry in crystals intermolecular aurophilic interactions (Au-Au distance = 3.

A dynamic tetranuclear gold(i)-cyclophane - gold(i)-centred chirality and fluxionality arising from an intramolecular shift of Au-S bonds.

A tetranuclear gold(i) complex [Au(μ-PAnP)(μ-L)] (PAnP = 9,10-bis(diphenylphosphino)anthracene and L = benzene-1,2-dithiolate) has been synthesized and characterised by multinuclear NMR and X-ray crystallography. The molecule has a cyclophane-like structure which can be considered to be composed of two [Au(μ-PAnP)(μ-L)] units held together by Au-S bonds and aurophilic interactions (Au-Au = 3.0712(2) Å).

Selective Hypochlorous Acid Detection by Electronic Tuning of Platinum-4,5-bis(diphenylphosphino)acridine-Thiolate Complexes.

Four [Pt(PNP)(L)] pincer complexes (PNP = 4,5-bis(diphenylphosphino)acridine; L = Cl (), CN (), benzenethiolate SPh (), and 4-thiolatobenzoic acid SPhCOH ()) were synthesized and structurally characterized. The oxidation of and by HOCl gave the corresponding sulfinate complexes (L = SOPh) and (L = SOPhCOH), which were characterized by X-ray crystallography. All of the complexes show intense acridine-based π → π* absorption at λ = 398-430 nm, but the spectra of and display low-energy absorptions at 525 and 482 nm, respectively, which are predominantly ligand (3p of S)-to-ligand (π* of acridine) charge transfer (CT) in nature.

Gold-Clip-Assisted Self-Assembly and Proton-Coupled Expansion-Contraction of a Cofacial Fe -Porphyrin Cage.

A molecular cage {Au (μ-PAnP) [Fe(H O) (TPyP)] (OTf) }(OTf) (1) composed of two cofacial Fe -porphyrin can be self-assembled from the gold clip [Au (PAnP)Cl ] and Fe (H O) (TPyP) (PAnP=9,10-bis(diphenylphosphino)anthracene, TPyP=meso-tetra(4-pyridyl)porphyrinato). The height of the cage is 8.579(3) Å.

Coupling d Ir(III) and d Pt(II) Chromophores.

Two classes of widely studied luminescent metal complexes are octahedral d (i.e., Ir) and square planar d (i.

Ir(2-phenylpyridine)2(benzene-1,2-dithiolate) anion as a diastereoselective metalloligand and nucleophile: stereoelectronic effect, spectroscopy, and computational study of the methylated and aurated complexes and their oxygenation products.

The anionic complex [Ir(2-phenylpyridine)2(benzene-1,2-dithiolate)](-) ([IrSS](-)) is a nucleophile and metalloligand that reacts with methyl iodide and AuPR3(+) (R = Ph or Et) to form S-methylated complexes (thiother-thiolate and dithiother complexes) and S-aurated complexes, respectively. The reactions are completely diastereselective, producing only the enantiomers ΛS and ΔR or ΛSS and ΔRR. The diastereoselectivity is stereoelectronically controlled by the orientation of the highest occupied molecular orbital (HOMO) of [IrSS](-) arising from filled dπ-pπ antibonding interactions, and the chirality of the iridium ion.

Synthesis and spectroscopy of anionic cyclometalated iridium(III)-dithiolate and -sulfinates--effect of sulfur dioxygenation on electronic structure and luminescence.

A new anionic heteroleptic Ir(III)-dithiolate complex Ir(ppy)2(benzene-1,2-dithiolate) (ppy = 2-phenylpyridine, [IrSS](-)) undergoes very fast air oxidation to form a monosulfinate complex [IrSSO2](-), which can be further dioxygenated by O2 or H2O2 to give a disulfinate complex [IrSO2SO2](-), which has been characterized by X-ray crystallography. The dioxygenation is accompanied by changes in the electronic structures of the complexes, leading to blue shift of emission from [IrSS](-) (λ(max) = 665 nm) to [IrSSO2](-) (λ(max) = 556 nm) and to [IrSO2SO2](-) (λ(max) = 460 nm). The molecular and electronic structures of the complexes are probed by DFT calculations.

Metallacyclophanes of 1,6-bis(diphenylphosphino)pyrene: excimeric emission and effect of oxygen on stability of the rings.

1,6-Bis(diphenylphosphino)pyrene (L) was reacted with Ag(I) and Cu(I) ions to form metallacyclophanes [Ag(2)L(2)(OTf)(2)] (1), [Cu(2)L(2)(MeCN)(4)](2+) (2), and [Cu(2)L(2)I(2)] (3) which consisted of two cofacial pyrenyl rings. 1 and 2 exhibited intramolecular excimeric emissions which along with the UV-vis absorption were invoked in understanding the solution dynamics of the metallocyclophanes. The metallacyclophanes were stable toward ring-opening dissociation at concentration as low as 10(-7) M.

Photooxidation of a platinum-anthracene pincer complex: formation and structures of Pt(II)-anthrone and -ketal complexes.

Irradiating the cyclometalated pincer complex Pt(II)(DPA)Cl (1, DPA = 1,8-bis(diphenylphosphino)anthracene) in the presence of O(2) led to three sequential oxidations of the anthracenyl ring. The first photoproduct, a Pt(II)-9,10-endoperoxide complex, was converted photochemically to a Pt(II)-9-hydroxyanthrone complex A which was further oxygenated to a Pt(II)-hemiketal (B). The oxidation of A, which could be accelerated by light irradiation, probably involved a Pt(II)-anthraquinone intermediate.

Synthesis and electrical characterization of oligo(phenylene ethynylene) molecular wires coordinated to transition metal complexes.

Organometallic wires are interesting alternatives to conventional molecular wires based on a pure organic system because of the presence of d orbitals in the transition metal complex. However, synthetic problems, such as decreased stability of the compounds when labile metal complexes are present, often impede their isolation in a pure state and preclude a rapid development of such hybrid molecular wires. In this work, we show that preassembled self-assembled monolayers (SAM) based on pyridine-terminated 1-((4-acetylthiophenyl)ethynyl)-4-((4-pyridyl)ethynyl)benzene can act as a template for the architectural build up of a second layer of transition metal complexes to form an array of organometallic molecular wires on gold.

Templated assembly of a pseudorotaxane of gold rectangles.

A nanoscopic pseudorotaxane (1)2 subset2 composed of the gold rectangle [Au4(mu-PAnP)2(mu-bipy)2](OTf)4 and the linear template 4,4'-bis(9''-anthryl)biphenyl was assembled (PAnP = 9,10-bis(diphenylphosphino)anthracene); bipy = 4,4'-bipyridine).

Self-assembly, structures, and solution dynamics of emissive silver metallacycles and helices.

Reactions of 9,10-bis(diphenylphosphino)anthracene (PAnP) and AgX (X = OTf-, ClO4-, PF6-, and BF4-) led to luminescent Ag-PAnP complexes with rich structural diversity. Helical polymers [Ag(mu-PAnP)(CH3CN)X]n (X = OTf-, ClO4-, and PF6-) and discrete binuclear [Ag2(mu-PAnP)2(CH3CN)4](PF6)2, trinuclear [Ag3(mu-PAnP)3 supersetBF4](BF4)2, and tetranuclear [Ag4(mu-PAnP)4 superset(ClO4)2](ClO4)2 metallacycles were isolated from different solvents. The tri- and tetranuclear metallacycles exhibited novel puckered-ring and saddlelike structures.

Self-assembly and molecular recognition of a luminescent gold rectangle.

A luminescent molecular rectangle [Au(4)(micro-PAnP)(2)(micro-bipy)(2)](OTf)(4) (1.(OTf)(4)) (PAnP = 9,10-bis(diphenylphosphino)anthracene, bipy = 4,4'-bipyridine, X = NO(3)(-) or OTf(-)), synthesized from the self-assembly of the molecular "clip" Au(2)(micro-PAnP)(OTf)(2) and bipy, shows a large rectangular cavity of 7.921(3) x 16.

Novel luminescent tetranuclear and pentanuclear copper(I)-dithiolates.

Tetranuclear [Cu(4)mu(2)-dppm)(3)(mu(2)-mu(2)-NS(2))(mu(2)-mu(4)-NS(2))] (1) and pentanuclear [Cu(5)(mu(2)-dppm)(4)(mu(3)-mu-(3)-NS(2))(2)]PF(6) (2.PF(6)) (dppm = bis(diphenylphoshino)methane, NS(2)(2)(-) = 1,8-naphthalenedithiolate) were synthesized from the reactions between NS(2)(2)(-) and [Cu(2)(mu(2)-dppm)(2)(CH(3)CN)(2)](PF(6))(2). Compound 1 features a square Cu(4) core capped by a 5-coordinate S atom while 2.

First examples of Au(I)-X-Ag(I) halonium cations (X = Cl and Br).

Novel {[(mu-PAnP)(AuX)2]2Ag}+SbF6- halonium ions (X = Cl, Br; PAnP = 9,10-bis(diphenylphosphino)anthracene) were synthesized from the reactions between (mu-PAnP)(AuX)2 and 1/2 mol equiv of AgSbF6. The compounds feature an unprecedented distorted Au4X4 dodecahedron which encapsulates a silver(I) ion at its center. The halonium ions are stabilized by collective actions of metallophilic Au-Ag, aromatic pi-pi, and Ag-X interactions.

A Luminescent Gold Ring That Flips Like Cyclohexane.

A chair of gold: Analogous to cyclohexane, the trinuclear gold ring [Au (PAnP) ][ClO ] (PAnP=9,10-bis(diphenylphosphino)anthracene) shows a chair conformation and diastereotopic axial and equatorial phenyl rings. Variable temperature and 2D EXSY NMR studies reveal that the gold ring undergoes cyclohexane-like ring inversion (enantiomerization) in solution. In addition, the gold ring exhibits intense excimeric emission at room temperature.