Polymerization of Styrene by Neutral Ni (II) Acetylide Complex

Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyrene obtained was a syndio-rich atactic polymer and its weight-average molecular weight reached 279000. The mechanism of the polymerization was discussed and a radical mechanism was proposed.

Luminescent Tetranuclear Copper(I) Phenylacetylide Complex with Cyclohexyl Isocyanide

Depolymerizing copper(I) phenylacetylide [Cu(C≡CPh)]n with cyclohexyl isocy- anide (CNCy) gave a tetranuclear copper(I) complex Cu4(CNCy)4(μ-η1-C≡CPh)2(μ3-η1,η1, η2-C≡ CPh)2. Crystal data: C30H32Cu2N2, Mr = 547.66, space group P1, a = 8.6448(1), b = 11.5772(2), c = 14.6666(4) ?, α = 88.387(2), β = 86.826(2), γ = 68.222(1)°, V = 1360.97(5) ?3, Z = 2, F(000) = 568, Dc = 1.336 g/cm3, μ = 1.582 mm-1, the final R = 0.0629 and wR = 0.1282 for 3257 observed reflections with I > 2σ(I). The phenylacetylide adopts μ-η1 and μ3-η1,η1,η2 bonding modes. The compound shows intense luminescence in the solid state.

POLYMERIZATION OF A NEW SUBSTITUTED ACETYLENE BEARING A FURAN RING WITH PALLADIUM ACETYLIDE CATALYSTS

A substituted polyacetylene bearing a furan ring, poly(2-propynyl 2-furoate) (PPF), was synthesized for the first time with palladium acetylide complex catalysts in CHCl3 at 60°C to give a soluble and stable polymer with a yield of ca. 75%. Some features for polymerization of 2-propynyl 2-furoate are described and discussed. The resulting polymer was characterized by IR, GPC and 1H-NMR analysis.

Tuning the Excited-state Properties of Cyclometalated Platinum(II) Complexes of 6-Phenyl-2,2′-bipyridine by Ancillary Acetylide Ligand

A series of luminescent cyclometalated platinum(II) complexes, (C^N^N)Pt(C≡CR) [HC^N^N=4 (4 tolyl) 6 phenyl 2,2′ bipyridine; R=4 chlorophenyl (1), phenyl (2) and 4 tolyl (3)], were synthesized, and their spectroscopic properties have been examined. These complexes are brightly emissive both in fluid solution and in the solid state, attributed to triplet metal to ligand charge transfer ( 3MLCT) state. The excited state energy can be tuned by ancillary acetylide ligands. The emission lifetimes in dichloro^methane solution at room temperature were up to 1 64 μs and the emission quantum yields were in the range of 0 03-0 15.

Solution-Processable Platinum-Acetylide-based Small Molecular Bulk Heterojunction Solar Cells

Two new solution-processable A＇-D-≡-Pt（PEt3）2-≡-D-A＇ structured molecules, namely, CNPT and DRPT, were synthesized and characterized for photovoltaic applications. Their optoelectronic properties were investigated by UV-vis absorption and cyclic voltammograms. Grazing-incidence wide-angle X-ray scattering and resonant soft X-ray scattering studies revealed that the DIO additive could enhance the crystallization of CNPT and reduce the size of phase separation of CNPT：PC71BM blends, while the addition of DIO showed little influence on the crystal- lization and morphology of the DRPT：PC71BM blends. Processing with the DIO additive, CNPT：PC71BM based solar cells showed a best power conversion efficiency of 1.4%, with a Jsc of 4.14 mA·cm^-2, a Voc of 0.75 V, and a fill factor of 45.4%.

A Novel Proton Sensor with Luminescence and Color Signaling Based on Platinum(II) Terpyridyl Acetylide Complex

A novel sensitive probe for proton based on platinum(II) terpyridyl acetylide complex by monitoring the changes both in luminescence and color is described.

An unexpected tetranuclear Li_2Cr_2 trimethylsilylacetylide complex bridged by two μ_3-pyrazolates

A tetranuclear Li2Cr2 acetylide precursor complex, [Li(Tp)crm(c=CSiMe3)2(/,t3-pz)]2· (n-pentane)2 (Tp = hydridotris(pyra- zolyl)borate, pz = pyrazolate) (1) has been synthesized and characterized. The X-ray structure analysis shows that the complex contains a Li2Cr2 core bridged by two ,u3-pyrazolates. The magnetic data exhibit the existence of weak antiferromagnetic in- teraction in the cluster.

Nafion-Induced Metal-Metal Interactions in a Platinum(II) Terpyridyl Acetylide Complex:a Luminescent Sensor for Detection of Volatile Organic Compounds

The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with max at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candi-date for polar VOC.

Syntheses and Crystal Structures of Silver(I) Complexes by Depolymerizing [Ag(C≡CPh)]_n with a NP_3 Ligand

Two silver(I) complexes were prepared by the reaction of [Ag(C≡CPh)]n with NP3 [NP3 = N(CH2CH2PPh2)3] or with NP3 and [Cu(CH3CN)4]ClO4. Complex 1 [(Ag2Cl(NP3)2)(Ag5- (C≡CPh)6)] contains both NP3 and PhC≡C- ligands. The complex cation is (Ag2Cl(NP3)2)+, in which two Ag(NP3)+ cations were bridged by a Cl- donor. The anion is (Ag5(C≡CPh)6)-, where five Ag+ ions are linked by six C≡CPh- to form a pentanuclear cluster. Complex 2 only contains NP3 ligand, where the silver center adopts a trigonal-bipyramidal geometry. Crystal data for 1: C133H116Ag7Cl3- N2P6, Mr = 2789.54, triclinic, space group P1, a = 13.0780(2), b = 15.3678(2), c = 31.2041(3) ?, α = 91.3928(7), β = 90.9328(8), γ = 96.0244(4)o, V = 6233.8(1) ?3, T = 293(2) K, Z = 2, Dc = 1.486 g/cm3, F(000) = 2796, μ = 1.266 mm-1, the final R = 0.0746 and wR = 0.1953 for 16475 observed reflections with I > 2σ(I). Crystal data for 2: C42H42AgClNO4P3, Mr = 861.00, trigonal, space group R3, a = 17.451(1), b = 17.451(1), c = 11.3985(7) ?, V = 3006.0(3) ?3, T = 293(2) K, Z = 3, Dc = 1.427 g/cm3, F(000) = 1326, μ = 0.731 mm-1, the final R = 0.0251 and wR = 0.0663 for 1499 observed reflections with I > 2σ(I).

POLYMERIZATION OF p-DIETHYNYLBENZENE INITIATED BY Ni(C≡CC_6H_4C≡CH)_2(PPH_3)_2

Homogeneous polymerization of p-diethynylbenzene initiated by nickel acetylide Ni(C ≡ C C_6H_4 C ≡ CH)_2(PPh_3)_2has been investigated in terms of different solvents, addition agents, atmosphere gases, catalyst concentrations, monomerconcentrations and polymerization temperatures. The yield and catalytic efficiency approach 88% and 11. 1 kg polymer/molNi, respectively, under the optimum conditions: [cat] = 0.01 mol/L, [M] = 1.0 mol/L, NEt_3/cat (mol ratio) = 3～5, 1,4-dioxane/toluene (volume ratio) = 1 and T = 25℃ for 5 h. The polymerization rate equation can be expressed as R_p =k_p[M][cat]~2, where k_p= 0.47 L^2. mol^(-2)·S^(-1) (25℃). The overall polymerization activation energy was found to be203 kJ·mol^(-1). Poly(p-diethynylbenzene) so obtained is soluble in THF, CHCl_3 and toluene with weight-average molecularweights as high as 27, 100 and a rich-trans extended π-conjugated polyene chain structure with pendent groups ofp-C_6H_4C≡CH.

Theoretical studies of structures and spectroscopic properties of [(tpy)(bpy)RuC≡CC_6H_4R]^+(tpy = 2,2′:6′,2″-terpyridine, bpy = 2,2′-bipyridine; R = F, Cl, H, Me and OMe)

A series of polypyridine ruthenium （II） acetylide complexes, [（tpy）（bpy）RuC≡CC6H4R]^＋ （tpy = 2,2＇：6＇,2＂-terpyridine, bpy = 2,2＇-bipyridine; R = F （1）, C1 （2）, H （3）, Me （4） and OMe （5）） are investigated theoretically to explore their electronic structures and spectroscopic properties. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of the complexes in acetonitrile solution are also obtained by using TDDFT （B3LYP） method associated with the CPCM model. The calculations show that the energy levels of HOMOs for 1-5 are sensitive to the substituent on phenylacetylide ligand and increase with the same order of the electron-donating ability of the substituents; however, those of polypyridine-based LUMOs vary slightly. The lowest-energy absorptions and emissions for 1-5 are progressively red-shifted in the order of 1 ~ 2 〈 3 〈 4 〈 5 when the electron-donating groups are introduced into the phenylacetylide [igand. The phosphorescence of 1 are attributed to {[dxz（Ru） ＋π（C≡C）]→[π^＊（tpy）]} （3MLCT/3LLCT） transition, whereas those of 2-5 are originated from { [dxz/dxy（Ru）＋ π（C ≡C）＋g（C6H4R）] → [＊（tpy/bpy）] } （3MLCT/3LLCT） transitions.

Synthesis and Luminescent Properties of Platinum-Containing Polyynes with Tetraacetylenic 9,9-Dihexylfluorene Units

Soluble platinum（Ⅱ） polyyne polymers trans-{Pt-[P（C4H8N）3]2（C≡C）2R（C≡C）2-}n and trans-{Pt-[P（C4H3O）3]2（C ≡C）2R（C ≡ C）2- }n （R = 9,9-dihexylfluorene-2,7-diyl） have been prepared in good yields by CuI-catalyzed polymerization involving the dehydrohalogenating coupling of trans-{PtCl2[P（C4H8N）3]2} and trans-{PtC12[P （C4H3O）312} with H（C≡C）2R（C≡C）2H, respectively. We report the optical spectroscopy of these polyplatinaynes. The influence of the heavy metal atom in these metal alkynyl systems on the intersystem crossing rate and the spatial extent of lowest singlet and triplet excitons was systematically characterized. Our investigations indicate that the organic triplet emissions can be harvested by the heavy-atom effect which enables efficient intersystem crossing from the S1 singlet excited state to the T1 triplet excited state.

Metallated conjugation in small-sized-molecular donors for solution-processed organic solar cells

Four metallated conjugated oligothiophenes, S-1, S-2, S-3 and S-4, with platinum（II） aryleneethynylenes as the electron-rich building block were synthesized to investigate their physicochemical and photovoltaic properties. These small molecules possess fairly low-lying HOMO energy levels which match with the LUMO energy level of the electron acceptor PC70BM （[6,6]-phenyl-C71-butyric acid methyl ester）. Using the simple process of spin-coating solution fabrication technique, S-I：PC70BM （1：4, w/w） based organic solar cells exhibiting a high Voc of 0.913 V, with a PCE value of 0.88% were developed. In contrast, the OSC device based on S-2：PC70BM （3：7, w/w） displayed a higher PCE of 1.59% with a higher Jsc value of 5.89 mA cm^-2. The device based on S-4：PCToBM （1：4, w/w） exhibited a PCE value of 1.56%, with a Voc of 0.917 V.

Polymerization of styrene by Novel Ni(Ⅱ)- and Pd(Ⅱ)-based complexes

The catalytic activities of nine neutral nickel and palladium a-acetylide complexes [M=(C=CR)2(PR'3)2)M=Ni,Pd; R=Ph,CH2OH,CH2OOCH3,CH2OOCPh,CH2OOCPhOH-o; R'=Ph,Bu] are compared.Among them,Ni(Cs=CPh)2-(PBuj)2 shows the highest catalytic activity and gives the polystyrene with high molecular weight(Mw=188800)and a syndio-rich microstructure.The catalytic behavior of transition metal acetylides is related to metal,phosphine,and alkynyl ligands bonded to the metal atoms.