Donor-acceptor conjugated cooligomers for single molecule solar cells

Five novel donor-acceptor(D-A) conjugated cooligomers(F4B-hP,F5B-hP,F5B2[1,2]-hP,F5B2[1,3]-hP and F7B2[1,2]-hP) were synthesized.The absorption spectra of the cooligomers cover a wide range from 300 nm to 630 nm.The cooligomers could form films featured by alternating D-A lamellar nanostructures with the periods relative to the molecular lengths after thermal annealing or solvent vapor annealing.Single molecule solar cells were fabricated,and F5B-hP exhibited the best device performance.When the film of F5B-hP was thermally annealed,a power conversion efficiency(PCE) of 1.56% was realized.With solvent vapor annealing,the PCE could be further improved to 1.72% with a short-circuit current(J SC) of 5.76 mA/cm 2,an open-circuit voltage(V OC) of 0.87 V and a fill factor(FF) of 0.34.     

Lanthanide-catalyzed cyclocarbonylation and cyclothiocarbonylation: a facile synthesis of benzannulated 1,3-diheteroatom five- and six-membered heterocycles

<正>NMR spectra were recorded in CDCl3 or DMSO-d6 on a Bruker Avance 400 operating at 400 MHz with TMS as internal standard. 1H-benzo[d]imidazol-2(3H)-one(3aa) [1]: 1H NMR(400 MHz, DMSO-d6) δ 10.5(s, 2 H, NH), 6.90(s, 4H)(aromatic CH). 13 C NMR(400 MHz, DMSO-d6) δ 155.7, 130.1, 120.9, 108.9. NH HN O3 aa 1-(2-Aminophenyl)-3-phenylurea(3aa′) [2]: 1H NMR(400 MHz, DMSO-d6) δ 8.75(s, 1H), 7.71(s, 1H)(CONH), 7.44(d, J = 8.0 Hz, 2H), 7.33(d, J = 7.8 Hz, 1H), 7.26(t, J = 7.7 Hz, 2H), 6.94(t, J = 7.4 Hz, 1H), 6.84(t, J = 7.4 Hz, 1H), 6.74(d, J = 7.8 Hz, 1H), 6.57(t, J = 7.4 Hz, 1H)(aromatic CH), 4.78(s, 2H)(NH2). 13 C NMR(400 MHz, DMSO-d6) δ 153.6, 141.4, 140.6, 129.2, 125.2, 124.8, 124.2,121.9, 118.4, 117.3, 116.4.     

反气相色谱法表征离子液体1-乙基-3-甲基咪唑六氟磷酸盐的溶解度参数（英文）

采用反气相色谱法(IGC)表征了离子液体1-乙基-3-甲基咪唑六氟磷酸盐([EMIM]PF_6)在343.15-373.15 K温度范围内的溶解度参数。各温度下溶解度参数分别为20.76(J/cm~3)~(0.5)(343.15 K),20.21(J/cm~3)~(0.5)(353.15 K),19.73(J/cm~3)~(0.5)(363.15 K),19.24(J/cm~3)~(0.5)(373.15 K)。然后,通过外推法得到[EMIM]PF_6在室温(298.15 K)时的溶解度参数为23.01(J/cm~3)~(0.5)。同时,测定了探针溶剂与[EMIM]PF_6之间的质量分数活度系数、无限稀释活度系数和Flory-Huggins相互作用参数等热力学参数。结果表明,n-C_6,n-C_7,n-C_8,n-C_9和四氢呋喃为[EMIM]PF_6的不良溶剂;而苯、甲苯、乙醇、甲醇、二氯甲烷、丙酮、乙酸乙酯、氯仿、乙醚、四氯化碳、乙酸甲酯和环己烷为[EMIM]PF_6的良溶剂。     

新型取代基炔类分子的合成及其与B(C6F5)3的反应

合成了5种不同取代基的炔类化合物Mes2HSiC≡CPh(1,Mes=2,4,6-Me3C6H2)、[tBuC(NAr)2]GeC≡CPh(2,Ar=2,6-iPr2C6H3)、[PhC(NtBu)2]SnC≡CPPh2(3)、[HC(CMe)2(NAr)2]Sn C≡CPPh2(4)和[HC(CMe)2(NAr)2]ZnC≡CPPh2(5),研究了这些化合物与B(C6F5)3的反应.在与B(C6F5)3的反应中,1和2均发生1,1-碳硼化反应生成烯烃化合物(Ph)(Mes2HSi)C=C(C6F5)B(C6F5)2 (6)和{[tBuC(NAr)2]Ge}(Ph)C=C(C6F5)B(C6F5)2 (7), 7是一种GeⅡ/B松散Lewis酸碱对化合物;3~5则都发生B(C6F5)3与配体金属基的位置交换、进而配体金属基转换键合PPh2的反应,分别生成新颖的分子内双性离子炔烃化合物[PhC(NtBu)2]SnP(Ph2)C≡CB(C6F5)3 (8)、[HC(CMe)2(NAr)2]SnP(Ph2)C≡CB(C6F5)3(9)、[HC(CMe)2(NAr)2]ZnP(Ph2)C≡CB(C6F5)3 (10).文中还讨论了反应机理.     

高氯酸锂与4-叔丁基苯并-15-冠-5配合物的远红外位移

冠醚化合物对金属离子具有特定的络合作用 [1,2 ] .在冠醚萃取分离锂同位素过程中 ,4-叔丁基苯并 -1 5 -冠 -5 (4 -t-BB1 5 C5 )是锂同位素效应较大且最接近实用的多醚之一 .它容易合成[3] ,而且已有若干萃取研究[4～ 6 ] .本文合成了高氯酸锂与 4-叔丁基苯并 -1 5 -冠 -5配合物 ,测定了若干表征值和远红外位移 ,并根据已有的理论框架[7] 算得配合物的相对约化配分函数比 [(s/s′) f ]org和碘苯 -水溶液两相平衡过程中锂同位素分离系数 α.为在冠醚体系的锂同位素分离研究中应用红外光谱取代质谱 ,直接测定和计算(1 +εp)值提供了可能性 .…     

Solvothermal Synthesis and Characterization of [TM(1,2-dap)_3]HgSb_2Se_5(TM = Co,Fe)with a Chain Structure

One organic-decorated quanternaery [TM(1,2-dap)3]Hg Sb2Se5(1,2-dap = 1,2-dianinopropane, TM = Co(1), Fe(2)) compound has been solvothermally synthesized. The compounds crystallize in triclinic space group P 1, with a = 11.248(6), b = 11.542(7), c = 12.180(12) ?, V =1268.7(16) ?~3, Z = 2, F(000) = 1010 for 1 and a = 11.311(5), b = 11.558(5), c = 12.180(9) ?, V =1276.5(12) ?~3, Z = 2, F(000) = 1008 for 2. The crystal structure consists of one-dimensional anionics chains composed of Hg Se4 tetrahedra and SbSe_3 trigonal pyramids sharing corners and[TM(dap)_3]~(2+) cations. The [HgSb_2Se+5~(2-)]∞ anionic chains run along the [001] direction, and are surrounded by the [TM(dap)_3]~(2+) cations. Meanwhile, 8-ring [Hg_2Sb_2Se_4] and 6-ring [HgSb_2Se_2] are alternately found. The compounds were structurally characterized by elemental analysis,thermogravimetric analysis, infrared spectroscopy and UV-Vis diffuse reflectance spectroscopy.     

Synthesis of O-(2-[~(18)F]fluoroethyl)-L-tyrosine and its biological evaluation in B16 melanoma-bearing mice as PET tracer for tumor imaging

O-(2-[18F]fluoroethyl) -L-tyrosine([18F]FET) ,a fluorine-18 labeled analogue of tyrosine,has been syn-thesized and biologically evaluated in tumor-bearing mice. The whole synthesis procedure is com-pleted within 50 min. The radiochemical yield is about 40%(no decay corrected) and radiochemical purity more than 97% after simplified solid phase extraction. [18F]FET shows rapid,high uptake and long retention in the tumor as well as low uptake in the brain. The ratios of tumor-to-muscle(T/M) and tumor-to-blood(T/B) of [18F]FET are similar to those of [18F]FDG,but the ratios of tumor-to-brain(T/Br) are 2-3 times higher than that of [18F]FDG. Autoradiography of [18F]FET demonstrates a remarkable accumulation in melanoma with high contrast. It appears to be a probable competitive candidate for melanoma imaging with PET.     

Highly efficient nickel/phosphine catalyzed cross-couplings of diarylborinic acids with aryl tosylates and sulfamates

<正>4-Methoxy-4′-methylbiphenyl(3aa) [1] MeO White solid(0.324 g, 82% from aryl tosylate, 0.356 g, 90% from aryl sulfamate); m.p. 111–112 °C; 1H NMR(400 MHz,CDCl3) δ 7.50(d, J = 8.4 Hz, 2H), 7.44(d, J = 8.0 Hz, 2H), 7.21(d, J = 8.0 Hz, 2H), 6.95(d, J = 8.8 Hz, 2H), 3.82(s, 3H), 2.37(s, 3H); 13 C NMR(100 MHz, CDCl3) δ 159.0, 138.0, 136.4, 133.8, 129.5, 128.0, 126.6, 114.2, 55.4, 21.1. 4,4′-Dimethylbiphenyl(3ab) [1] White solid(0.320 g, 88% from aryl tosylate, 0.346 g, 95% from aryl sulfamate); m.p. 122–123 °C; 1H NMR(400 MHz,CDCl3) δ 7.47(d, J = 8.0 Hz, 4H), 7.22(d, J = 8.0 Hz, 4H), 2.37(s, 6H); 13 C NMR(100 MHz, CDCl3) δ 138.4, 136.8, 129.5, 126.9, 21.2.     

THE MOLECULAR AND CRYSTAL STRUCTURE OF [Et4N]2[Fe2S2（NO）4]

<正> The compound [Et_4N]_2[Fe_2S_2(NO)_4] (M_r=556.36) crystallizes in the monoclinic,space group P 2_1/n with a=9. 688(3), b=10. 882(2), c=12. 625(2), β=97. 86(3)°, Z=2, V=1318. 4, D_c=1. 40g/cm~3, ;μ(MoK_a)=12. 8cm~(-1) and F(000)=588. The final R=0. 028 and R_w=0. 029 for 2041 reflections (I≥3σ(I)).The crystals of [Et_4N]_2[Fe_2S_2(NO)_4] consist of discrete cations [Et_4N]~+ and anions     

A Nove Asymmetric ent—Kauranoid Dimer from Isodon enanderianus

Further investigation on the aerial parts of Isodon enanderianus afforded a novel asymmetric ent-kauranoid dimer,enanderi-nanin J(1).The structure of the dimer was elucidated by means of spectroscopic methods (including 2D NMR tecniques ),Enanderinanin J was a dimer of xerophilusin A and probably formed by [4 2] cycloaddition.     

Stability,acidity and interaction properties of [Bmim][SbF_6] coupled with concentrated sulfuric acid

Ionic liquid coupled with strong acid systems presents considerable promise in some catalytic fields.In the present work,the multiple complex systems composed by 98 wt%concentrated sulfuric acid and[Bmim][SbF_6]were investigated in the terms of stability,acidity and interaction properties.It was found that acidolysis of[Bmim][SbF_6]occurred in the 98 wt%concentrated sulfuric acid accompanied by HF releasing and SbF_6~ degrading to[SbF_(6-y)XHSO_4]_y]~-.The species after acidolysis in the multiple complex systems were checked and confirmed by electrospray ionization mass spectrometry(ESI-MS),Fourier transform infrared spectroscopy(FT-IR),~1H NMR and ~(19)F NMR.Acidity increased slightly with less than 1 wt%[Bmim][SbF_6]addition,while decreased with more proportion,which was determined based on the Hammett acidity functions H_0,using ~(13)C NMR.The strong hydrogen bond S-O-H…F of interaction among the multiple complex systems was confirmed by molecular dynamic simulation.     

Synthesis, characterization and magnetism of binuclear cobalt (II) complexes bridged by tetracarboxylato groups

Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti     

Structure and Magnetic Property of an Oxygenand Carboxamide-bridged One-dimensional Iron（Ⅲ） Complex [Fe2（μ-O）（bpb）2]n

The structure of the title complex [Fe2(μ-O)(bpb)2]n (bpb 2=1,2-bis(pyridine-2carboxamido) benzenate) has been characterized by single-crystal X-ray diffraction analysis.The complex (C36 H24 Fe2N8O5,Mr=760.33) crystallizes in the monoclinic space group P2 1/c with a=8.4615(17),b=33.704(7),c=11.173(2),β=91.12(3)o,V=3185.7(11)3,Z=4,D c=1.585 g/cm 3,μ(MoK)=0.970 mm-1,F(000)=1552,R int=0.0381,the final R=0.0454 and wR=0.1114.The magnetic susceptibilities of the complex have been examined in the temperature range of 2-300 K.The magnetic data were fitted to give the parameters of J d=-77.7(9) and J c=-11.5(6) cm-1.     

稀土乙酰丙酮-α,β,γ,δ-四邻硝基苯基卟啉钬的合成

本文首次合成出镧系乙酰丙酮-α,β,γ,δ-四邻硝基苯基卟啉配合物Ho(o-NO_2)TPPacac(Ⅰ),并简单地讨论了它的性质。 反应中间物三水乙酰丙酮配合物Ho(acac)_3·3H_2O用文献方法[1]合成和纯制。α,β,γ,δ-四邻硝基苯基卟啉(o-NO_2)TPP用改进的Kim,J.B.法[2]     

硫代草酸铁(Ⅲ)配合物的酸性水解动力学

本文研究了配合物KCaFe(SC_2O_3)_3·3H_2O在30、40、50℃的Clark-Lubs缓冲溶液中的酸性水解动力学。测定了不同温度和酸度的准一级速度常数K_(th),K_(th)。与[H~( 1)呈直线关系,K_(th)=K_1[H~ ] k_2,K_1是与平衡常数和速度常数k_1有关的常数,k_2为速度常数。提出的反应机制认为是通过不对称配位原子形成共轭酸,再发生铁-硫键破裂,酸性水解的活化参数△H~(?)=78.81±1.18kJ.mol~(-1),△S~(?)=-46.67±0.68J·K~(-1)·mol~(-1),与文献报导的具有不对称配位原子螯合物的酸性催化离解的数值相近。     

Zero- and One-dimensional Organic-inorganic Hybrid Compounds Based on Monovacant Keggin Polyoxotungstatesa

Two new organic-inorganic hybrid mono-transition-metal-substituted polyoxometalates [Ni(2,2'-bipy)3]3[Ni(H2O)SiW11O39]·11H2O 1 and [Cu(dien)(H2O)][Cu(dien)(H2O)2]2-[CuSiW11O39]·5.5H2O 2 (2,2'-bipy = 2,2'-bipyridine, dien = diethylenetriamine) have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, magnetic properties, and IR spectrum. Crystal data for 1: monoclinic, space group P21/n, a = 17.492(3), b = 33.481(5), c = 20.493(3) A, β = 101.894(3)°, Dc = 2.563 mg/A3, F(000) = 8440,μ = 11.454 mm-1 and Z = 4; and those for 2: monoclinic, space group P21/n, a = 11.114(3), b = 22.803(7), c = 22.468(7) A, β = 97.896(6)°, Dc = 4.036 mg/A3, F(000) = 6140,μ = 23.942 mm-1 and Z = 4. The study on the magnetic susceptibility of 2 demonstrates the presence of ferromagnetic interaction.     

发现氘的科学家尤里

同位素这个名词的西文isotope是英国人索迪(F.Soddy,1877-1956)于1911年开始使用的。后来,另一位英国人阿斯顿(F.W.Aston,1877-1945),在1919年制成了质谱仪,可以用来分离不同质量的粒子,并且测定它们的质量。     

《影像科学与光化学》参考文献格式要求

<正>一.专著作者(全部).书名.版本(第1版不著录).出版地点:出版单位,出版年.起止页码.示例:[1]Griffiths L.Colour and Constitution of Organic Molecules[M].London:Academic Press,1976.[2]Forster T W.In:Rurton M,Kirby-Smith J S,Magee J I,eds.Comparative Effects of Radiation[M].Vol.30,3rd ed.New York and London:Wiley,1960.300.     

《影像科学与光化学》参考文献格式要求

正一.专著作者(全部).书名.版本(第1版不著录).出版地点:出版单位,出版年.起止页码.示例:[1]Griffiths L.Colour and Constitution of Organic Molecules[M].London:Academic Press,1976.[2]Forster T W.In:Rurton M,Kirby-Smith J S,Magee J I,eds.Comparative Effects of Radiation[M].Vol.30,3rd ed.New York and London:Wiley,1960.300.[3]王德海,江棂.紫外光固化材料理论与应用[M].北京:科学出版社,2001.316-319.     

全氟辛基磺酰亚胺稀土(Ⅲ)催化氟两相Friedel-Crafts烷基化反应

制备了全氟辛基磺酰亚胺盐(M[N(SO2C8F17)2]n,n:3,4),并用于催化氟两相烷基化反应。考察了催化剂种类、反应时间、反应温度和催化剂用量对烷基化反应的影响,同时探讨了Yb[N(SO2C8F17)2]3对烷基化试剂摩尔比为0.2%时,催化烷基化试剂与不同芳烃的反应,表明Yb[N(SO2C8F17)2]3是一种有效的烷基化催化剂。含有催化剂的氟相通过简单的相分离后,可回收利用。氟相重复使用5次,其催化活性降低不大。