Synthesis,Structure and Fluorescence of Olefin-Copper(Ⅰ) Coordination Polymers

The organic olefin ligand 2,5-dimethyl-1-(4-vinyl-benzyl)-piperazine reacts with CuX(X = Cl, Br) to obtain two novel olefin-copper(I) coordination polymers [C_(15)H_(22)N_2Cu_2Cl_3]n(1) and [C_(15)H_(20)N_2Cu_2Br_2]n(2). There are two types of CuX warp structures that have never been seen before in the presence of methanol under solvothermal conditions. The new olefin-copper(I) coordination complex crystallizes in the monoclinic space group P21/c to obtain compounds 1 and 2. Its unique green fluorescence effect can be applied to the LED field.     

Structures and Spectroscopic Properties of(1)Dipyridine Quinoxaline with Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ)

The interaction of Hg(Ⅱ), Cu(Ⅰ) and Ag(Ⅰ) with dipyridine quinoxaline ligand 2,3-bis(2-pyridyl)quinoxaline(DPQ) were investigated, and three new complexes have been synthesized and characterized. Complex 1 exhibits a 0D dual-core structure, complex 2 is a 0D tetra nuclear case based on a dual-core Cu unit, and complex 3 shows a one-dimensional pipeline structure. Furthermore, the optical properties of complex and DPQ were also investigated, and the results showed that the fluorescence intensity of complexes was weaker than that of ligand DPQ.     

Synthesis,Structure and Photochromism of a New Diarylethene and Its Ag(Ⅰ) Complex

A new symmetric diarylethene containing cyano group was synthesized and structurally characterized by elemental analysis,IR,1 H NMR and X-ray single-crystal diffraction.It belongs to the monoclinic system,space group C2/c with a = 18.848(6),b = 8.561(2),c = 16.875(5) ?,β = 100.398(6)o,V = 1344.6(11) ?~3,Z = 4,μ = 0.262 mm~(-1),Dc = 1.415 g/cm~3,M_r = 570.56,F(000) = 1160,the final R = 0.0808 and wR = 0.2107 with I 2σ(I).The two thienyls adopt reactive anti-parallel conformation and the carbon distance of photocyclization is 3.57 ?.The neighboring molecules are stacked closely with C–H…F hydrogen bonding.In addition,the photochromism of the new compound was investigated in solvents with different polarity and PMMA film.The alternative photo-irradiation of 254 nm light and ≥550 visible light can induce the reversible photo-cyclization and photo-reversion with the color interconversion between colorlessness and blue.In THF solution,the λ_(max) of diarylethene in PSS in visible band is 585 nm.The diarylethene further reacted with AgBF_4 in benzene to give rise to complex 1,which was structurally characterized by elemental analysis,IR,ESI-MS and TG.1 demonstrated reversible photochromism in both solution and PMMA film.The complexation of metal ions with diarylethene leads to a minor red-shift of the λ_(max) of 1 in THF in PSS to 590 nm.     

Phase behaviour and microstructures of microemulsions(Ⅰ)

By the orthogonal design,the optimal formation conditions for the middle-phase microemulsions in the system dioctadeeyldimethylammornum chloride (DODMAC)/ sodium dodecyl sulfate (SDS)/n-butanol/n-hep-ane/brine were obtained as follows.Investigations have been made on the effects of the concentrations of NaCl and n-butanol(1.0%-14.0%),the rantos of W to Wshs and the kinds of alcohols (n-propanol,n-butanol,and n-pentanol) on the formation,the phase behavtour,the ultralow interfacial tensions,the optimal salinity (S*),and the length of salinity (S).Some rules and data were worked out about the formation and characteristics of the middle-phase microemulsions.The mi-crostruenres of the middle-phase microemulsions were also studied by using FT-IR,ESR,and freeze fracture electron microscopy techmques The results from the three methods show that the microstructures of the middle-phase mi-croemnlsions undergo the change from O/W to bicontinuous(B C.) and to W/O.The distribution rule of the orga-mzed molecule ass     

Synthesis,Crystal Structure,and Photo-and Electro-luminescence of a TADF Cu(Ⅰ) Complex

A four-coordinate mononuclear cuprous complex [Cu(ac1m)POP]BF_4·0.5(C_6H_(14))· 0.5(C_2H_5OH)(1, ac1 m = 2-(2-ethoxyphenyl)-1-phenyl-1H-imidazo[4,5-f][1,10]phenanthroline, POP = bis[2-(dipenylphosphino)phenyl]ether) was synthesized and characterized by elemental analysis, NMR, UV-vis, cyclic voltammetry and X-ray single-crystal structure analysis. It crystallizes in monoclinic space group P2_1/c with a = 17.0546(19), b = 15.4650(17), c = 23.685(2) ?, β = 104.007(11)°, V = 6061.1(12) ?~3, Z = 4, M_r = 1171.46, D_c = 1.284 g/cm~3, F(000) = 2432, μ = 1.50 mm~(–1), GOOF = 1.070, the final R = 0.059 and wR = 0.1640 for 8952 observed reflections with I 2σ(Ⅰ). Compound 1 is composed of a BF4-anion and a [Cu(ac1m)POP]~+ cation. The Cu(Ⅰ) ion adopts a tetrahedral coordination geometry defined by two nitrogen and two phosphorous atoms. The complex exhibits yellow luminescence with maximum emission peaks at 546 nm, lifetimes 15.1 μs and quantum yields(ф = 0.130) at room temperature. The complex displays thermally activated delayed fluorescence(TADF) at room temperature, which is proved experimentally and theoretically. And the organic light-emitting diode(OLED) with 1 as the light emitting material has the maximum current efficiency of 5.86 cd/A and the highest brightness of 3215 cd/m~2.     

Synthesis,Crystal Structure and Photoluminescence of a Three-coordinate Ag(Ⅰ) Complex

A three-coordinate Ag(I) complex, [Ag(Mepzpy)(PAr3)]BF4·H2O(1, Mepzpy = 3-methyl-1-(2-pyridyl)pyrazole, PAr3 = tri(o-tolyl)phosphine), was synthesized from the reaction of Ag(CH3CN)4BF4, PAr3 and Mepzpy in CH3 CN at room temperature. The compound was characterized by UV-vis, NMR and X-ray single-crystal structure analysis. It crystallizes in triclinic space group P1 with a = 10.2251(5), b = 10.6014(5), c = 15.7012(5) , α = 92.963(3), β = 92.641(3), γ = 114.647(4)o, V = 1540.6(1) 3, Z = 2, Mr = 676.24, Dc = 1.458 g/cm3, F(000) = 688, μ = 6.187 mm-1, GOOF = 1.038, the final R = 0.0530 and w R = 0.1493 for 6371 observed reflections with I 2σ(I). Compound 1 is ionic. It is composed of a BF4- anion and a [Ag(Mepzpy)(PAr3)]+ cation. The Ag(I) ion adopts a distorted trigonal pyramidal coordination geometry defined by two nitrogen atoms and a phosphorous atom. The complex emits blue luminescence with maximum peaks at 470 nm in solid state at room temperature.     

Design, synthesis and antitumor activity of 3-substituted quinolone derivatives (Ⅰ)

A series of quinolone derivatives containing benzimidazole, benzoxazole or benzothiazole ring were synthesized. The cytotoxicity of 12 new compounds was evaluated in KB, Be17402, A2780 and HT-29 cell lines. Most of synthesized compounds showed moderate inhibitory activity against cancer cells. The inhibitory activities of 6k, against KB and A2780 tumor cells are comparable to that of topotecan, one of topoisomerase I inhibitors.     

Synthesis and Characterization of One-dimensional and Two-Dimensional Porphyrin Polymers (Ⅰ)

Porphyrin polymers are of interest in relation to conductive materials[1, 2], catalysts for photosynthetic charge separation[3], or the fundamental features in biological systems[4]. There have been many versatile studies about them[5.6]. The one-dimensional "Shish Kebab"porphyrin polymers synthesized with a new method different from those reported and Schiff-base porphyrin polymers with two-dimensional nano-structure have provided a new field of study. The present paper covers highly ordered…     

Synthesis,Structural Characterization and Catalytic Activity of Copper(Ⅰ) Complexes with Triphenylphosphine and Pyridine Derivatives

Two new Cu(Ⅰ) complexes [CuCl(3-PyOH)(PPh_3)_2](1) and [Cu_2(μ-Cl)_2(4-Stpy)(Ph_3P)_3](2)(PyOH = hydroxypyridine; stpy = styrylpyridine) with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945(7), b = 37.266(2), c = 10.9461(7) ?, β = 116.0750(10)°, V = 3625.3(4) ?~3, Z = 4, D_c = 1.350 Mg/cm~(-3), μ = 0.801 mm~(-1), F(000) = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections(I 2σ(I)), R(all data) = 0.0413, wR(all data) = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290(3), b = 20.388(5), c = 24.092(6) ?, β = 102.028(4)°, V = 5424(2) ?~3, Z = 4, D_c = 1.428 Mg/cm~(-3), μ = 1.016 mm~(-1), F(000) = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections(I 2σ(I)), R(all data) = 0.0716, wR(all data) = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu(I) complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.     

Synthesis of the Natural Products Resveratrol (Ⅰ) and Isorhapotogenin (Ⅱ)

ResveratrolIandisorhapotigeninIIaretwonaturalproductswithmanybiologicalactivities',andtheirtotalsynthesis'havebeenreported.LinMaoetal3flrstisolatedthemfromG.parvofOlium,atraditionalChineseherbusedtotreatrheumatoidarthritis,ulcerbleedingandbronchitis.Inanattempttopreparecnoughsamplesfortlirtherpharmacologicalevaluation,severalsynthesisstrategieshavebeenexplored'.WchavcdevelopedtwosyntheticapproachesofIandIIinSchemelandScheme2,respectivcly.Startingfrom3,5-dihydroxybenzoicacid,thecompound2wa…     

Synthesis,Crystal Structure and Photoluminescence of a TADF Dinuclear Cu(Ⅰ) Complex

A binuclear Cu(Ⅰ) complex[Cu(PCNP)(mepypz)]_2(BF_4)_2 (1,PCNP=2,6-bis(diphenylphosphine)-benzonitrile,mepypz=2-methyl-6-(1H-pyrazol-3-yl)-pyridine was synthesized from the reaction of Cu(CH_3CN)_4BF_4,PCNP and mepypz in CH_2Cl_2 at room temperature.The compound was characterized by NMR,UV-vis and X-ray single-crystal structure analysis.It crystallizes in monoclinic space group P2_1/c with a=14.0139(5),b=11.8149(3),c=27.1248(10)?,β=96.686(4)°,V=4460.6(3)?~3,Z=2,M_r=1561.97,D_c=1.163 g/cm~3,F(000)=1600.0,μ=1.774 mm~(–1),GOOF=1.071,the final R=0.0523 and w R=0.1412 for 7919 observed reflections with I2σ(I).The Cu atoms in the complex are four-coordinated and adopt a distorted tetrahedral coordination geometry.In the solid state,the complex exhibits yellowish-green emission with a peak wavelength of 546 nm,a lifetime of 390μs,and a quantum yield of 0.45 at room temperature.The temperature-dependent investigation of luminescent properties suggests that the complex emits thermally activated delayed fluorescence (TADF) at room temperature.     

Syntheses,Structures,and Luminescent Properties of Zinc(Ⅱ) and Silver(Ⅰ) Complexes Based on 1-(4?-Carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole

Two novel coordination compounds, [Zn(CBPP)2(H2O)2]·3H2O(1) and[Ag(CBPP)·2H2O](2)(HCBPP = 1-(4?-carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole), were hydrothermally synthesized and characterized. Compound 1 crystallizes in monoclinic, space group C2 with a = 26.221(4), b = 8.4211(7), c = 14.295(3) ?, β = 114.561(8)o, V = 2705.9(2) ?3, Dc = 1.587 g/cm3, C28H28Cl2N8O9 Zn, Mr = 685.97 F(000) = 1416, μ(Mo Kα) = 0.926 mm-1, Z = 4, R = 0.0287, w R = 0.1076 for 2818 observed reflections(I 2σ(I)), and R = 0.0300, w R = 0.1110 for all data. In 1, each deprotonated CBPP-ligand with a bidentate coordination mode connects two Zn(II) atoms to generate a 1D helical chain along the b axis. The adjacent chains intersect with each other through hinged Zn(II) ions to build up an interesting two-dimensional network. Compound 2 crystallizes in monoclinic, space group P21/n with a = 6.3544(1), b = 11.7195(3), c = 19.3188(4) ?, β = 94.297(2)o, V = 1434.64(5) ?3, Dc = 1.894 g/cm3, C14H13 Ag N4O4, Mr = 409.15 F(000) = 816, μ(Mo Kα) = 11.536 mm-1, Z = 4, R = 0.0456 and w R = 0.1184 for 2402 observed reflections(I 2σ(I)), and R = 0.0517, w R = 0.1275 for all data. In 2, each ligand binds two Ag(I) atoms in a tridentate coordination mode to form an infinite zigzag chain. Their thermal and photoluminescent properties were also investigated.     

Facile Syntheses of (±)-Curcuphenol, (±)-Curcudiol, (±)-Curcuhydroquinone,and (±)-Curcuquinone

The syntheses of (±)-curcuphenol 1, (±)-curcudiol 2, (±)-curcuhydroquinone 3, and (±)-curcuquinone 4 have been achieved. The key steps involved in the syntheses were the Reformatsky reaction and hydrogenation reaction.     

Peptidase Activities of Tripeptidyl Peptidase Ⅰ(TPP Ⅰ): Exopeptidase and Endopeptidase

The defect of TPP Ⅰ causes a disease, late infantile neuronal ceroid lipofuscinosis(LINCL, CLN2). To investigate the bio-activity of tripeptidyl peptidase Ⅰ(TPP Ⅰ) from rat kidneys, the effects of digestion of angiotensin Ⅱ(Ang Ⅱ) and a synthetic endo-type substrate(Gly1-Lys-Pro-Iie-Pro5-Phe-Phe-Arg-Leu-Lys10) via TPP Ⅰ were analyzed by HPLC and TOF-MS. The data suggest that the degradation rate of Ang Ⅱ can reach 18.2% by the rat TPP Ⅰ and DRV(Asp-Arg-Val) can be released from N-termini of Ang Ⅱ within 16 h. In addition, the synthetic endo-type substrate is cleaved at the same position between Phe6 and Phe7. Accordingly, TPP Ⅰ shows two kinds of peptidase activities. One is a tripeptidyl peptidase activity and the other is a pepstatin insensitive carboxyl endopeptidase activity. Tripeptidyl peptidase activity and pepstatin insensitive carboxyl endopeptidase activity seem to be dual phases of one enzyme, TPP Ⅰ.     

Cu(Ⅰ) and Cu (Ⅱ) helical complexes formed with oligobipyridine ligand

A new asymmetric oligobipyridine ligand, 1-(5'-methyl-2, 2'-bipyridin-5-yl)-2-(6'-methyl-2, 2'-bipyridin-6-yl)ethane (L), in which the bipyridine units are bridged by CH_2CH_2 at 5, 6'-position has been synthesized. The ligand L reacts with Cu(Ⅰ) and Cu(Ⅱ) ions giving double-stranded helical complexes [Cu_2~ⅠL_2] (ClO_4)_2·Et_2O (1) and [Cu_2~ⅡL_2 (OH) (H_2O)][ClO_4]_3(2), respectively. Complexes 1 and 2 were characterized by X-ray diffraction analyses, ES-MS, ESR and cyclic voltammetry, etc. Differing from the oligobipyridine ligands bridged by CH_2CH_2 at 6,6'-or 5,5'-position, the ligand L not only forms a double-stranded helicate with Cu(Ⅰ) ion, but also gives a double-stranded helicate with Cu(Ⅱ) ion. The results show that the linkage mode of the spacer group to the bipyridine units exerts a great impact on the formation of helix.     

Total synthesis of (±)-maistemonine, (±)-stemonamide, and (±)-isomaistemonine

A full account of the total synthesis of (±)-maistemonine, (±)-stemonamide, and (±)-isomaistemonine is presented. Two approaches have been developed to construct the basic pyrrolo[1,2-a]azepine core of the Stemona alkaloids, featuring a tandem semipinacol/Schmidt rearrangement of a secondary azide and a highly stereoselectively desymmetrizing intramolecular Schmidt reaction, respectively. To build the common spiro-γ-butyrolactone, a new protocol was carried out by utilizing an intramolecular ketone-ester condensation as the key transformation. The vicinal butyrolactone moiety of (±)-maistemonine was stereoselectively introduced via a one-pot procedure involving the epimerization at C-3 and carbonyl allylation/lactonization. Moreover, (±)-stemonamide was divergently synthesized from a common intermediate, and (±)-isomaistemonine was obtained via the epimerization of (±)-maistemonine at C-12.     

Luminescent Cu(Ⅰ) and Ag(Ⅰ) coordination polymers:Fast phosphorescence or thermally activated delayed fluorescence

By applying two donor-acceptor motif molecules,5,10-di(pyridin-4-yl)-5,10-dihydrophenazine(LI)and 10,10'-di(pyridin-3-yl)-10 H,10'H-9,9'-spiroacridine(L2),as ligands and CuI/AgCF_3 CO_2 as metal salt,we synthesized three coordination polymers,namely,{Cu_4(L1)_2 I_4}(CP1),{Cu(L2)I-CHCl_3}(CP2) and{Ag(L2)CO_2 CF_3·CHCl_3}(CP3).X-ray crystallographic analysis revealed that three coordination polymers all feature one-dimensional(1 D) linear chains which are consisting of molecular boxlike units.In comparison with low photoluminescence quantum yield(PLQY) of two ligands,three coordination polymers.CP1,CP2 and CP3,present more intense photoluminescence with PLQY of 15%,46% and 34% at room temperature respectively.The PL emission of CP1 and CP2 at room temperature could be attributed to the fast phosphorescence with lifetime both around 5 μs due to effective intersystem crossing(ISC).Whilst,it is worth noting that CP3 exhibit thermally activated delayed fluorescence(TADF) emission at room temperature.     

Synthesis and Crystal Structure of a Dicopper(Ⅰ) Complex with Bis(diphenylphosphino)methane and Diethyldithiocarbamate

1 INTRODUCTION Dithiocarbamate derivatives and their metal complexes are extremely versatile compounds which have been used, for example, in the treatment of alcoholism, sarcoma cell and as possible pro- tection against the lethal effect of X-rays etc[1]. Owing to the striking structure features and diversified applications of the metal complexes with dithiocarbamate[2～6], it is of theoretical and practical significance to study the coordination chemistry much more adequately. The meta…     

Silver(Ⅰ) Complexes with Mixed Diphosphine Ligands:Syntheses,Characterization and Spectroscopic Properties

Two novel silver(I) complexes [Ag(DPEphos)(dppe)]Cl O4(1) and [Ag(DPEphos)-(dppe)]SCN(2)(DPEphos = bis[2-(diphenylphosphino)phenyl]ether, dppe = bis(diphenylphosphino)ethane) are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821(12), b = 12.6620(11), c = 36.025(3) ?, β = 112.633(2)°, V = 6265.7(9) ?3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F(000) = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021(13), b = 12.6100(11), c = 35.920(3) ?, β = 112.852(2)°, V = 6220.2(9) ?3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F(000) = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections(I 2σ(I)). In mono-nuclear complexes 1 and 2, the Ag(I) atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals(doublets or triplets) which can be attributed to the coupling of the 107,109Ag–31P(from DPEphos or dppe ligand). All the emission peaks of these complexes are attributed to ligand-centered(π-π*) transitions.     

Syntheses and Crystal Structures of Hg(Ⅱ) and Ag(Ⅰ) Complexes Containing 2-Acetylpyridine-paminobenzoylhydrazone Ligand

The two complexes [HgI_2L](DMF)(1) and [AgL_2](ClO_4)(CH_3CN)(2) were synthesized from the reaction of Schiff base ligand(2-acetylpyridine-p-aminobenzoylhydrazone)(L) with HgI_2 or AgClO_4 respectively. The compounds are characterized by ~1H NMR,FTIR and elemental analysis. The structures of the ligand and two complexes are measured via single-crystal X-ray diffraction. In these two complexes,the structures are both distorted triangular bipyramids with five-coordinated centers.