Doping Copper(I) in Ag Cluster for Circularly Polarized OLEDs with External Quantum Efficiency of 26.7 .

Hetero-metal doping or substitution to create alloy clusters is a highly appealing strategy for improving physicochemical characteristics as well as tailoring optical and electronic properties, although high-yield synthesis of alloy clusters with precise positioning of doped metals is a daunting challenge. Herein, we manifest rational synthesis of chiral alloy cluster enantiomers R/S-AgCu in 85 %-87 % yield by replacing one Ag(I) atom with Cu(I) in homometallic clusters R/S-Ag, achieving circularly polarized luminescence (CPL) with a quantum yield beyond 90 %. As a small energy gap (ca.

Synergistic coordination of diphosphine with primary and tertiary phosphorus centers: Ultrastable icosidodecahedral Ag nanoclusters with metallic aromaticity.

As versatile ligands with extraordinary coordination capabilities, RPH (R = alkyl or aryl) are rarely used in constructing metal nanoclusters due to their volatility, toxicity, spontaneous flammability, and susceptibility to oxidation. In this work, we designed a primary and tertiary phosphorus-bound diphosphine chelator (2-PhPCHPH) to create ultrastable silver nanoclusters with metallic aromaticity. By controlling the deprotonation rate of 2-PhPCHPH and adjusting the templates, we successfully synthesized two near-infrared emissive nanoclusters, and , which have analogous icosidodecahedral Ag shells with an symmetry.

Naphthalimide-Modified Clusters for Red-Emitting Devices with High Color Purity.

Conventional fluorescent materials frequently exhibit narrow-band emissions with a small full width at half-maximum (fwhm) due to localized-state characteristics, but electroluminescence is less efficient owing to the utilization of only singlet excitons. In this work, taking advantage of naphthalimide (NAI)-acetylide derivatives with a rigid planar structure and localized transition characteristics, we elaborately designed two mononuclear Pt(II) complexes with weak double emissions of fluorescence and phosphorescence. Taking them as synthetic precursors, we prepared three PtAu heteronuclear clusters and successfully attained highly efficient narrow-band red phosphorescence with the fwhm below 30 nm.

The single pregnancy predicting model of 1 minute Apgar score less than 7 after preterm birth: A retrospective study.

Preterm delivery is greatly associated with perinatal mortality and morbidity, while there is no objective way to identify high-risk newborns currently. This study aimed at discovering the risk factor for Apgar score less than 7 at 1 minute of preterm neonates born with vaginal delivery. A retrospective study was performed in single pregnancy women with a vaginal delivery before 37 weeks of gestation.

Elaborate Design of d-d Heteronuclear Phosphors for Ultrahigh-Efficiency Solution-Processed Organic Light-Emitting Diodes.

Highly soluble d-d heteronuclear phosphors afford an alternative approach to achieve high-efficiency organic light-emitting diodes (OLEDs) through a solution process. In this work, four highly phosphorescent d-d heteronuclear complexes with significant Pt-Au interactions were prepared. By judicious selection of sterically hindered and π-conjugated substituents in triphosphine ligands, the phosphorescence is dramatically promoted through effectively prohibiting nonradiative thermal relaxation with an efficiency of 0.

Elaborate Design of AgAu Cluster [2]Catenane Phosphors for High-Efficiency Light-Emitting Devices.

In this work, rational design of highly soluble and phosphorescent Ag-Au cluster complexes with exceptional [2]catenane structures is conducted using 1,8-diethynyl-9-carbazole (Hdecz) as a rigid U-shaped ligand with a distinguished hole-transport character. The self-assembly reaction of Hdecz, Au, and Ag generated phosphorescent AgAu cluster (Φ = 0.22 in CHCl) with Hdecz having a free ethynyl (-C≡CH) group.

Coordination-Bond-Driven Dissolution-Recrystallization Structural Transformation with the Expansion of Cuprous Halide Aggregate.

Metal-organic frameworks (MOFs) with cuprous-halide-aggregates have shown superiority as organic LED (OLED) and semiconductor materials, while engineering MOF flexibility by involving the expansion of cuprous aggregates remains a great challenge. In this particular work, a dissolution-recrystallization structural transformation (DRST) with the dramatic growth of Cu-I aggregates, from 2D to 3D has been successfully realized. The unsaturated coordination nodes (2-positional nitrogen atoms) in have been demonstrated to be the driven force for DRST to via the formation of coordination bonds.

Synthesis, structures and luminescence properties of amine-bis(N-heterocyclic carbene) copper(i) and silver(i) complexes.

A series of Ag(i) and Cu(i) complexes [Ag3(L1)2][PF6]3 (8), [Ag3(L2)2][PF6]3 (9), [Cu(L1)][PF6] (10) and [Cu(L2)][PF6] (11) have been synthesized by reactions of the tridentate amine-bis(N-heterocyclic carbene) ligand precursors [H2L1][PF6]2 (6) and [H2L2][PF6]2 (7) with Ag2O and Cu2O, respectively. Complexes 10 and 11 can also be obtained by transmetalation of 8 and 9, respectively, with 3.0 equiv.

An unprecedented photochromic system with cis-oriented dithienyl-dithiolenes supported by metal chelation.

4,5-Bis(2-methyl-5-phenylthiophen-3-yl)-1,3-dithiol-2-one (L1o) was elaborately designed to afford dithienyl-dithiolene as a new photochromic ligand. We describe herein the preparation and characterization of unprecedented photochromic dithienyl-dithiolene complexes with cis-orientation of dithienylethene (DTE) stabilized by metal chelation instead of conventional cyclopentene. The treatment of L1o with sodium methoxide in methanol afforded a disodium salt of dithiolate dianion, which reacts with M(dppe)Cl (dppe = 1,2-bis(diphenylphosphino)ethane, M = Ni, Pd) to give neutral compounds M(dppe)(dithiolate) as established by X-ray crystallography.

Syntheses, characterization and electrochemical and spectroscopic properties of ruthenium-iron complexes of 2,3,5,6-tetrakis(2-pyridyl)pyrazine and ferrocene-acetylide ligands.

Heterodimetallic Ru-Fe complexes [(tppz)(PPh3)2RuL](ClO4) (L = C[triple bond, length as m-dash]CFc, [](ClO4); C[triple bond, length as m-dash]C-C6H4-C[triple bond, length as m-dash]CFc), [](ClO4); C[triple bond, length as m-dash]C-C6H4-C6H4-C[triple bond, length as m-dash]CFc, [](ClO4)) were synthesized by the reactions of [(tppz)(PPh3)2RuCl](ClO4) (tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine) with ferrocence-acetylide ligands and characterized by ESI-MS, and (1)H and (31)P NMR spectroscopies. The structure of [](PF6) was determined by X-ray crystallography. The electrochemical studies show that compounds [](ClO4)-[](ClO4) possess two widely separated anodic peaks, ascribable to one-electron oxidation of Fc and Ru(II), respectively.

Multistate and Multicolor Photochromism through Selective Cycloreversion in Asymmetric Platinum(II) Complexes with Two Different Dithienylethene-Acetylides.

Four asymmetric bis(dithienylethene-acetylide) platinum(II) complexes trans-Pt(PEt3)2(L1o)(L5o) (1oo), trans-Pt(PEt3)2(L2o)(L5o) (2oo), trans-Pt(PEt3)2(L3o)(L5o) (3oo), and trans-Pt(PEt3)2(L4o)(L5o) (4oo) with two different dithienylethene-acetylides (L1o-L5o) were designed to modulate stepwise, multistate, and multicolor photochromism by modifying ring-closure absorption wavelengths. Upon irradiation under UV light, 1oo converts only to 1oc without the observation of 1co and dually ring-closed species 1cc. In contrast, both mixed ring-open/closed species oc and co as well as dually ring-closed species cc are observed upon UV light irradiation of 2oo-4oo, implying that a substantial stepwise photochromic process occurs following 2oo-4oo → 2oc-4oc/2co-4co → 2cc-4cc.

Modulating stepwise photochromism in platinum(II) complexes with dual dithienylethene-acetylides by a progressive red shift of ring-closure absorption.

To modulate stepwise photochromism by shifting ring-closure absorption of the dithienylethene (DTE) moiety, trans-Pt(PEt3)2(C≡C-DTE)2 [C≡C-DTE = L1o (1oo), L2o (2oo), L3o (3oo), and L4o (4oo)] and cis-Pt(PEt3)2(L4o)2 (5oo) with two identical DTE-acetylides were elaborately designed. With the gradual red shift of ring-closure absorption for L1c (441 nm) → L2c (510 nm) → L3c (556 nm) → L4c (602 nm), stepwise photochromism is increasingly facilitated in trans-Pt(PEt3)2(C≡C-DTE)2 following 1oo → 2oo → 3oo → 4oo. The conversion percentage of singly ring-closed 2co-4co to dually ring-closed 2cc-4cc at the photostationary state is progressively increased in the order 1cc (0%) → 2cc (18%) → 3cc (67%) → 4cc (100%).

Aggregation-induced phosphorescence of iridium(III) complexes with 2,2'-bipyridine-acylhydrazone and their highly selective recognition to Cu2+.

Two cationic cyclometallated iridium(III) complexes with 2,2'-bipyridine-acylhydrazone were synthesized and characterized by spectroscopic and photophysical measurements. They exhibit remarkable aggregation-induced phosphorescent emission (AIPE) phenomenon which is caused by the restriction of rapid isomerization of the C=N bond in the acylhydrazone moiety and are supported by TD-DFT studies. They also act as a significant 'off-on' luminescent switch for Cu(2+) which works as both catalyzer and oxidant in the sensing process, resulting in hydrolysis and cyclization products which are highly emissive.

Redox-modulated stepwise photochromism in a ruthenium complex with dual dithienylethene-acetylides.

Achieving stepwise photochromism in a combined molecule to access all of the possible ring-open/closed isomers is a challenge due to facile energy transfer from ring-open dithienylethene (DTE) to an adjacent ring-closed moiety that prohibits further photocyclization. The preparation, characterization, and photochromic properties of a bis(σ-acetylide) bonded ruthenium(II) complex 2oo and its oxidized form 2oo(+) with two identical DTE-acetylides (L1o) are described. Stepwise and dual photochromic reactions are successfully achieved in both 2oo and 2oo(+), in which the ring-closing absorption band of 2oo(+) shows an obvious blue-shift relative to 2oo.

Gold(I)-coordination triggered multistep and multiple photochromic reactions in multi-dithienylethene (DTE) systems.

The preparation, characterization, and photochromic properties of a mononuclear gold(I) complex (1oo) with two identical DTE-acetylides and a dinuclear gold(I) complex (2ooo) with both DTE-acetylide and DTE-diphosphine are described. Both gold(I) complexes exhibit multistep and multiple photocyclization/cycloreversion reactions. Particularly, four-state and four-color photochromic switch is successfully achieved for the dinuclear gold(I) complex upon irradiation with appropriate wavelengths of light.

An iridium(III) complex of oximated 2,2'-bipyridine as a sensitive phosphorescent sensor for hypochlorite.

The designed synthesis of a sensitive phosphorescent chemosensor [Ir(ppy)(2)(L1)](PF(6)) (1) (Hppy = 2-phenylpyridine, L1 = 4'-methyl-2,2'-bipyridyl-4-carbaldehyde oxime) was carried out for selective detection of hypochlorite (ClO(-)). Complex 1 is weakly emissive in solution at ambient temperature due likely to rapid isomerization of C=N-OH as an effective non-radiative decay process. When 1 reacts with ClO(-), however, the emission is remarkably enhanced, in which the oxime in L1 is converted to a carboxylic acid in L2 (4'-methyl-2,2'-bipyridine-4-carboxylic acid).

Sensitized luminescence in dinuclear lanthanide(III) complexes of bridging 8-hydroxyquinoline derivatives with different electronic properties.

Three new dinuclear lanthanide(III) complexes {Eu(hfac)(3)(H(2)O)}(2)(μ-HPhMq)(2) (2) and {Ln(hfac)(3)(H(2)O)}(2)(μ-HMe(2)NC(6)H(4)Mq)(2) (Ln = Eu, 3; Nd, 4) with 8-hydroxylquinoline derivatives in μ-phenol mode were synthesized and characterized, where hfac(-) = hexafluoroacetylacetonate, HPhMq = 2-methyl-5-phenylquinolin-8-ol, and HMe(2)C(6)H(4)Mq = 5-(4-(dimethylamino)phenyl)-2-methylquinolin-8-ol. Compared with that (400 nm) for {Eu(hfac)(3)}(2)(μ-HMq)(2) (1, HMq = 2-methy-8-hydroxylquinoline), the excitation wavelength for sensitized lanthanide luminescence is extended to ca. 420 nm for 2, and 500 nm for 4 by introducing a phenyl or 4-(dimethylamino)phenyl to 8-hydroxylquinoline.

A sensitive phosphorescent thiol chemosensor based on an iridium(III) complex with alpha,beta-unsaturated ketone functionalized 2,2'-bipyridyl ligand.

An iridium(III)-containing phosphorescent chemosensor Ir(ppy)(2)(L)(PF(6)) (1, ppy = 2-phenylpyridine) containing a 2,2'-bipyridyl ligand (L) functionalized with an alpha,beta-unsaturated ketone for selective detection of thiol was synthesized and characterized by spectroscopic and photophysical measurements. The structure of complex 1 was determined by X-ray crystallography. In order to get an insight into 1,4-addition reactions of thiol to complex 1, the adduct 2 from reaction of 1 with benzenethiol was successfully prepared and characterized.

Square structures and photophysical properties of Zn(2)Ln(2) complexes (Ln = Nd, Eu, Sm, Er, Yb).

Heterotetranuclear Zn(2)Ln(2) (Ln = Nd , Eu , Sm , Er , Yb ) complexes {Zn(2)(Mq)(2)(tpyO)(2)}{(Ln(hfac)(3))(2)} (HMq = 2-methyl-8-hydroxylquinoline, tpyOH = [2,2':6'2'']terpyridin-4'-ol, hfac = hexafluoroacetylacetonate) display novel square structures ligated by bifunctional ligands tpyO (mono- and tridentate) and Mq (chelating and bridging mu-phenoxo). These compounds exhibit sensitized lanthanide emission upon photo-excitation of ZnMq/tpy antenna chromophores. By virtue of the dual luminescence with complementary colors, the ZnMq/tpyO-based cyan emission and Sm(III)-centered orange luminescence are combined to generate a white-light emission in Zn(2)Sm(2) (4) complex.

Photochromic and electrochromic properties of oxo-centred triruthenium compounds with a dithienylethene bis(phosphine) ligand.

The reaction of 1,2-bis(5-(diphenylphosphino)-2-methylthien-3-yl) cyclopentene (PPh(2)-DTE-PPh(2)) with the triruthenium cluster precursor [Ru(3)O(OAc)(6)(py)(2)(CH(3)OH)](PF(6)) (1) gave monomeric or dimeric derivatives [Ru(3)O(OAc)(6)(py)(2){PPh(2)-DTE-PPh(2)}](PF(6)) ([2]PF(6)) and [{Ru(3)O(OAc)(6)(py)(2)}(2){mu-PPh(2)-DTE-PPh(2)}](PF(6))(2) ([3]PF(6)). Reduction of [2](+) and [3](2+) afforded one- or two-electron-reduced neutral products Ru(3)O(OAc)(6)(py)(2){PPh(2)-DTE-PPh(2)} (2) and {Ru(3)O(OAc)(6)(py)(2)}(2){mu-PPh(2)-DTE-PPh(2)} ()3, respectively. These triruthenium complexes show remarkable photochromism through photochemical ring-closing (UV light irradiation) and ring-opening (Vis light irradiation) processes as well as electrochromic properties through oxidation/reduction in the triruthenium cluster.

Systematic investigation on the coordination chemistry of a sulfonated monoazo dye: ligand-dominated d- and f-block derivatives.

Ten coordination compounds based on a sulfonated monoazo dye, formulated as M(H(2)O)(2)(4,4'-abs)(2) (M = Mn , Co , Cu , Zn , Cd and Pb ; 4,4'-abs = 4-aminoazobenzene-4'-sulfonic anion), Ag(4,4'-abs) (), [Ln(H(2)O)(phen)(2)(4,4'-abs)(3)].3H(2)O (Ln = Gd , Tb , and Ho ; phen = 1,10-phenanthroline), as well as the parent ligand L [(4,4'-Habs)(2).4H(2)O] and precursor NaL.

[Evaluation of the inhibitory effect of tripeptide tyroservatide on growth of human hepatocellular carcinoma using a hollow fiber assay].

Objective: To investigate the inhibitory effect of tyroservatide (YSV) on growth of hepatocellular carcinoma cells.

Methods: In vitro effects of YSV on five human hepatocellular carcinoma cell lines were assayed by MTS. In vivo effects of YSV on 5 human hepatocellular carcinoma cell lines were assayed by hollow fiber tumor model.

Sensitization of lanthanide luminescence by two different Pt-->Ln energy transfer pathways in PtLn3 heterotetranuclear complexes with 5-ethynyl-2,2'-bipyridine.

Reactions of 5-[2-(trimethylsilyl)-1-ethynyl]-2,2'-bipyridine (Me3SiC-Cbpy) with Pt(bpy)C12 (bpy = 2,2'-bipyridine) and Pt(bpyC[triple bond]C-C[triple bond]Cbpy)Cl2 (bpyC[triple bond]C-C[triple bond]Cbpy=bis(2,2'-bipyridin-5-yl)butadiyne) induced isolation of Pt(bpy)(C[triple bond]Cbpy)2 (1) and Pt(bpyC[triple bond]C-C[triple bond]Cbpy)(C[triple bond]Cbpy)2 (5), respectively. Incorporating Ln(hfac)3(H2O)2 (hfac = hexafluoroacetylacetone) with 1 or 5 gave the corresponding PtLn2 (Ln = Nd (2), Eu (3), Yb (4)) or PtLn3 arrays (Ln=Nd (6), Eu (7), Gd (8), Yb (9)). With excitation at 360 < or = lamda(ex)0 < or =480 nm, which is the MLCT absorption region of the Pt(2,2'-bipyridyl)(acetylide)2 chromophore, sensitized lanthanide luminescence is successfully attained by efficient Pt-->Ln energy transfer from the Pt(II) antenna chromophores.

Reversal effect of tyroservatide (YSV) tripeptide on multi-drug resistance in resistant human hepatocellular carcinoma cell line BEL-7402/5-FU.

Tyroservatide (YSV) is an active, low-molecular-weight polypeptide that has been shown to have antitumor effects on human hepatocellular carcinoma BEL-7402 cells in vitro and in vivo. Multi-drug resistance (MDR) represents a major obstacle to the success of cancer chemotherapy. To enhance the chemosensitivity of tumor cells, attention has been focused on MDR modulators.

Preparation, characterization, and photophysical properties of Pt-M (M = Ru, Re) heteronuclear complexes with 1,10-phenanthrolineethynyl ligands.

When 3-ethynyl-1,10-phenanthroline (HCCphen) or 3,8-diethynyl-1,10-phenanthroline (HCCphenCCH) is utilized as a bifunctional bridging ligand via stepwise molecular fabrication, a series of Pt-Ru and Pt-Re heteronuclear complexes composed of both platinum(II) terpyridyl acetylide chromophores and a Ru(phen)(bpy)2/Re(phen)(CO)3Cl subunit were prepared by complexation of one or two Pt((t)Bu3tpy)(2+) units to the mononuclear Ru(II) or Re(I) precursor through platinum acetylide sigma coordination. These Pt-Ru and Pt-Re complexes exhibit intense low-energy absorptions originating from both Pt- and Ru (Re)-based metal-to-ligand charge-transfer (MLCT) states in the near-visible region. They are strongly luminescent in both solid states and fluid solutions with a submicrosecond range of lifetimes and 0.