基于苯甲酸受体的咔唑染料敏化剂的合成和光电性能

选择N-正丁基咔唑作为电子给体,芴酮作为桥键,苯甲酸作为受体,通过桥键芴酮与给体和受体连接位置的改变,设计合成了两个咔唑染料4-(6-(N-正丁基咔唑-3-基)-9-氧-9H-芴-3-基)苯甲酸(HXL-3W)和4-(7-(N-正丁基咔唑-3-基)-9-氧-9H-芴-2-基)苯甲酸(HXL-4Z).对咔唑染料的光谱性能、电化学性能和光电转换性能进行了研究,并运用密度泛函理论(DFT)方法对其几何结构和紫外-可见光谱进行了优化计算.结果表明, HXL-4Z的吸收光谱呈现两个明显的π→π^*跃迁吸收峰和一个较小的对应于分子内电荷转移的吸收峰,而HXL-3W的吸收光谱则仅呈现一个π→π^*跃迁吸收峰,且摩尔吸光系数远小于HXL-4Z.可能是HXL-3W分子结构中给体和受体距离较近,张力较大,导致较差的分子平面性和分子内电荷转移.因而HXL-4Z的光吸收能力和电子注入效率较优,从而具有较好的光电转换效率(2.03%) (短路电流(J_SC) = 3.88 mA·cm^-2,开路电压(V_OC) = 700 mV,填充因子(FF) = 0.75).     

染料敏化太阳能电池TiO2电极的制备及电解质的影响

采用溶胶-凝胶水热法制备了锐钛矿型纳米晶TiO₂薄膜电极,在乙二醇碳酸酯(EC)/1,2-丙二醇碳酸酯(PC)电解液体系中,研究了I₂和KI含量对电极光电性能的影响,发现随着电解液中I₂含量的增加,电池的短路光电流呈现先增加后减小的趋势,但光电流增加和减少的幅度并不大,同时体系的暗电流不断增加,光电压不断下降;随着电解液中KI含量的增加,电池的短路光电流也不断增加,当KI的含量大于0.2 mol/L时,电池的短路光电流的增加的趋势减缓.并对电解液中I₂和KI含量对电池光电性能影响的原因进行了初步的探讨.     

P(VDF-HFP)基凝胶电解质染料敏化纳米TiO2薄膜太阳电池

采用循环伏安法(CV)研究了凝胶电解质中I₃-/I-氧化还原行为,凝胶电解质中I₃-/I-的表观扩散系数和相应的稳态扩散电流明显低于液体电解质.通过对阴/阳离子的结合能和孔穴阻塞作用的研究解释了凝胶电解质电导率较液体电解质发生变化的原因.制备的凝胶电解质电池具有较高的光电转换效率(6.6%),其短路电流密度(Jsc)仅比液体电解质电池低0.3-0.4 mA/cm²,电池效率也仅低约0.6%.     

双功能型吡啶基离子液体的性质及在染料敏化太阳电池中的应用

采用高压釜无溶剂法合成了一种吡啶碘离子液体1-乙基-4-叔丁基吡啶碘(TBEPI), 并将其应用到染料敏化太阳电池(DSC)中. 利用电化学阻抗谱(EIS)、循环伏安(CV)和傅里叶变换衰减全反射红外光谱(ATR-FTIR)研究了TBEPI作为碘源的电解质的电化学性质、在TiO₂膜上的吸附特性及抑制TiO₂/染料/电解质界面电子复合的动力学过程. 结果表明, TBEPI作为碘源可提供充足的碘离子, 其电解质的电导率、电化学窗口及氧化还原电对的扩散能力都满足电池工作的需要. TBEPI可有效吸附在TiO₂ 表面形成阻挡层, 抑制TiO₂/染料/电解质界面的电子复合过程, 与传统的以1,2-二甲基-3-丙基咪唑碘(DMPII)作为碘源的DSC相比, 光电转换效率(η)由7.1%提高到7.5%.     

1-甲基-3-己基咪唑碘在染料敏化太阳电池中的应用研究

利用超微铂电极和循环伏安法, 以及电化学阻抗谱研究了在1-甲基-3-己基咪唑碘(HMII)的3-甲氧基丙腈(MePN)溶液中I₃^－和I^－的氧化还原行为, 并对比了由不同浓度的I₂和HMII组成的电解质溶液对染料敏化纳米薄膜太阳电池(DSCs)光伏性能的影响. 发现以MePN为溶剂, 含1.0 mol•dm^－3 HMII, 0.12 mol•dm^－3 I₂, 0.10 mol•dm^－3 LiI和0.50 mol•dm^－3 4-叔丁基吡啶的电解质溶液, 其DSCs的短路光电流密度为14.06 mA•cm^－2, 开路电压为0.71 V, 填充因子为0.69, 光电转换效率达6.81%.     

辛氧基苯基取代的吡啶并[3,4-b]吡嗪染料的合成与光伏性能研究

为了进一步提高电池的开路电压, 把吡啶并吡嗪核上的甲氧基苯换成辛氧基苯, 设计合成了一系列以三苯胺为给体、辛氧基苯取代的吡啶并[3,4-b]吡嗪为辅助受体、噻吩(呋喃、苯)为π-链、氰基乙酸为受体的新型染料敏化剂(OPP-I～Ⅲ). 对OPP-I～Ⅲ的光电化学性质、器件性能以及电荷转移动力学等进行了系统的测试及研究. 实验结果表明, 用辛氧基取代甲氧基, 能有效减少染料在TiO₂表面的聚集, 同时能阻止电解质和TiO₂导带的接触, 抑制电荷复合, 提高了开路电压. 最后, 在AM 1.5(100 mW·cm^-2)光强条件下, OPP-I敏化的电池最大光电转换效率为 6.57%(短路电流为 11.7 mA·cm^-2, 开路电压为 717 mV, 填充因子为 0.78).     

Y2O3/TiO2 "核-壳"结构在染料敏化太阳电池中的应用

在纳米TiO₂多孔薄膜表面包覆超薄绝缘体,形成"核-壳"结构的势垒层,是目前染料敏化太阳电池（DSC）光阳极改性的研究热点之一.本文选取氧化钇（Y₂O₃）作为包覆层材料,采用浸渍法对纳米TiO₂多孔薄膜进行修饰,研究Y₂O₃包覆处理对TiO₂薄膜微观结构及能带结构的影响;将浸渍法制备得到的Y₂O₃/TiO₂"核-壳"结构光阳极应用于DSC中,研究了饣覆层对电子传输复合以及DSC光电转换性能的影响.结果表明,Y₂O₃包覆处理后,薄膜的平带电势负移,且电子复合得到有效抑制,电子寿命增大,电池的开路电压明显提高.研究表明,适量引入Y₂O₃可以达改善电池性能的目的.     

含二级供电基团的三苯胺类光敏染料合成及太阳能电池中的应用

以N,N-二甲基苯胺作为二级给电子单元, 合成两种具有不同长度共轭链的三苯胺类光敏染料XS19和XS22. 研究了它们的光物理与光电化学性质, 并将它们用作TiO₂纳米晶电极的光敏化剂引入太阳电池, 结果表明, N,N-二甲基苯胺的引入能够抑制染料敏化太阳能电池中的电子复合, 提高电池的光电转换效率. XS22表现出更好的光伏性能, 在AM1.5 (100 mW•cm^－2)的光强下, XS22敏化电池的开路电压(V_OC)为685 mV, 短路电流密度(J_SC)为9.6 mA•cm^－2, 填充因子(FF)为0.72, 总光电转换效率为4.7%.     

PEDOT的电化学合成及其在固态染料敏化太阳能电池中的应用研究

本工作主要围绕PEDOT的合成及其在固态染料敏化太阳能电池对电极中的应用开展研究,重点研究了循环伏安法电化学沉积过程中循环次数(10～50次)对PEDOT薄膜的形貌、厚度及光学性质的影响.通过红外光谱、SEM、紫外-可见吸收光谱表征了PEDOT的结构、形貌及光性质;通过J-V、动态调制光电流谱(IMPS)/光电压谱(IMVS)以及Tafel测试表征了基于PEDOT透明对电极染料敏化太阳能电池的光电化学性能.结果表明:采用循环伏安法电沉积合成PEDOT制备固态染料敏化太阳能电池对电极时,CV循环30～40次之间时可以获得最佳的光电性能,固态器件的光电转换效率为5.34%,这是因为在该条件下所制备的PEDOT具有均匀致密的表面、较好的光学性质以及较高的光电催化性能(J₀=2.51×10^-3A·cm^-2),使得器件可以获得较大的扩散系数(D_n=28.80μm²·ms^-1)和载流子扩散长度(L=21.41μm),有利于电荷的传输.当CV循环次数大于40次时,PED...     

过氧化钛配合物(PTC)体系在柔性染料敏化太阳能电池中的应用

本文利用水性过氧化钛配合物(peoxotitanium complex:PTC)前驱体可低温合成锐钛矿TiO₂溶胶的特性,将其用作柔性染料敏化太阳能电池(DSSC)中的光阳极材料的成膜助剂.研究发现:加入基于PTC制得的TiO₂溶胶可以明显提高DSSC的光电转换性能,在制备DSSC的浆料中加入10%(体积分数)的基于PTC制得的TiO₂溶胶后,电池的光电效率可以提升50%.我们进一步研究了光电转换效率的影响因素,结果表明,溶胶的加入量和反应时间均有一最佳值,当基于PTC的TiO₂溶胶添加量为10%,反应时间为9h,所得到电池的光电性能最好.     

Synthesis of (C5Me5)2(C5Me4H)UMe, (C5Me5)2(C5H5)UMe, and (C5Me5)2UMe[CH(SiMe3)2] from cationic metallocenes for the evaluation of sterically induced reduction

To probe the correlation of unusual (C5Me5)(1-) reactivity with steric crowding in complexes such as (C5Me5)3UMe and (C5Me5)3UCl, slightly less crowded (C5Me5)2(C5Me4H)UX analogues (X = Me, Cl) were synthesized and their reactivity was evaluated. The utility of the cationic precursors [(C5Me5)2UMe](1+), 1, and [(C5Me5)2UCl](1+), 2, in the synthesis of (C5Me5)2(C5Me4H)UMe, 3, and (C5Me5)2(C5Me4H)UCl, 4, was also explored. Since the use of precursor [(C5Me5)2UMe][MeBPh3], 1a, is complicated by the equilibrium between 1a and (C5Me5)2UMe2/BPh3, the reactivity of [(C5Me5)2UMe(OTf)]2, 1b, (OTf = O3SCF3) prepared from (C5Me5)2UMe2 and AgOTf, was also studied. Both 1a and 1b react with KC5Me4H to form 3. Complex 4 readily forms by addition of KC5Me4H to [(C5Me5)2UCl][MeBPh3], generated in situ from (C5Me5)2UMeCl and BPh3. Complex 1b was preferred to 1a for the synthesis of (C5Me5)2(C5H5)UMe, 5, and (C5Me5)2UMe[CH(SiMe3)2], 6, from KC5H5 and LiCH(SiMe3)2, respectively. Complex 6 is the first example of a mixed alkyl uranium metallocene complex. Sterically induced reduction (SIR) reactivity was not observed with 3-6 although the methyl displacements from the (C5Me5)(1-) ring plane for 3 are the closest observed to date to those of SIR-active complexes. The (1)H NMR spectra of 3 and 4 are unusual in that all of the (C5Me4H)(1-) methyl groups are inequivalent. This structural rigidity is consistent with density-functional theory calculations.     

Photochemical reactions of [CH2(eta5-C5H4)2][Rh(C2H4)2]2 with silanes: evidence for Si-C and C-H activation pathways

Photochemical reaction of [CH2(eta5-C5H4)2][Rh(C2H4)2]2 1 with dmso led to the stepwise formation of [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(dmso)] 2a and [CH2(eta5-C5H4)2][Rh(C2H4)(dmso)]2 2b. Photolysis of 1 with vinyltrimethylsilane ultimately yields three isomeric products of [CH2(eta5-C5H4)2][Rh(CH2=CHSiMe3)2]2, 3a, 3b and 3c which are differentiated by the relative orientations of the vinylsilane. When this reaction is undertaken in d6-benzene, H/D exchange between the solvent and the alpha-proton of the vinylsilane is revealed. In addition evidence for two isomers of the solvent complex [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(eta2-toluene)] was obtained in these and related experiments when the photolysis was completed at low temperature without substrate, although no evidence for H/D exchange was observed. Photolysis of 1 with Et3SiH yielded the sequential substitution products [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(SiEt3)H] 4a, [CH2(eta5-C5H4)2][Rh(C2H4)(SiEt3)H]2 4b, [CH2(eta5-C5H4)2][Rh(C2H4)(SiEt3)H][Rh(SiEt3)2(H)2] 4c and [CH2(eta5-C5H4)2][Rh(SiEt3)2(H)2]2 4d; deuteration of the alpha-ring proton sites, and all the silyl protons, of 4d was demonstrated in d6-benzene. This reaction is further complicated by the formation of two Si-C bond activation products, [CH2(eta5-C5H4)2][RhH(mu-SiEt2)]2 5 and [CH2(eta5-C5H4)2][(RhEt)(RhH)(mu-SiEt2)2] 6. Complex 5 was also produced when 1 was photolysed with Et2SiH2. When the photochemical reactions with Et3SiH were repeated at low temperatures, two isomers of the unstable C-H activation products, the vinyl hydrides [CH2(eta5-C5H4)2][{Rh(SiEt3)H}{Rh(SiEt3)}(mu-eta1,eta2-CH=CH2)] 7a and 7b, were obtained. Thermally, 4c was shown to form the ring substituted silyl migration products [(eta5-C5H4)CH2(C5H3SiEt3)][Rh(SiEt3)2(H)2]2 8 while 4b formed [CH2(C5H3SiEt3)2][Rh(SiEt3)2(H)2]2 (9a and 9b) upon reaction with excess silane. The corresponding photochemical reaction with Me3SiH yielded the expected products [CH2(eta5-C5H4)2][Rh(C2H4)2][Rh(C2H4)(SiMe3)H] 10a, [CH2(eta5-C5H4)2][Rh(C2H4)(SiMe3)H]2 10b, [CH2(eta5-C5H4)2][Rh(C2H4)(SiMe3)H][Rh(SiMe3)2(H)2] 10c and [CH2(eta5-C5H4)2][Rh(SiMe3)2(H)2]2 10d. However, three Si-C bond activation products, [CH2(eta5-C5H4)2][(RhMe)(RhH)(mu-SiMe2)2] 11, [CH2(eta5-C5H4)2][(Rh{SiMe3})(RhMe)(mu-SiMe2)2] 12 and [CH2(eta5-C5H4)2][(Rh{SiMe3})(RhH)(mu-SiMe2)2] 13 were also obtained in these reactions.     

Synthese von 3-Oxacholestanen

Successive treatment of 5α-cholestan-3-one ( 1 ) with O₂ under basic conditions and then NaBH₄ led to 5α-3-oxa-cholestan-2-one ( 5 ). Analogous reactions with 5β-cholestan-3-one ( 6 ) yielded 5α-4-oxa-cholestan-3-one ( 7 ) and 5 ξ-3-oxa-cholestan-4-one ( 8 ). 4-Cholesten-2-one ( 10 ), which was prepared starting from 4-cholesten-3-one, was isomerized by methanolic KOH to give a mixture of 5α-cholest-3-en-2-one ( 11 ) and 5β-cholest-3-en-2-one ( 12 ). 5β-Cholestane-2,3-dione ( 17 ) was synthesized from 4β-bromo-5β-cholestan-3-one ( 13 ). Ozonolysis of the dione 17 and subsequent NaBH₄ reduction of the oxidation product gave both 5β-2-oxa-cholestan-3-one ( 18 ) and 5β-3-oxa-cholestan-2-one ( 19 ).     

(四甲基二硅撑)二(3-三甲硅基环戊二烯基)四羰基二铁及其相关化合物的合成及结构

1,2-二(三甲硅基环戊二烯基)四甲基二硅烷与Fe(CO)5在二甲苯中于105～110℃反应除分离到少量标题化合物(Me2SiSiMe2)[η-(3-Me3SiC5H3Fe(CO)]2(μ-CO)2(5)外,主要是生成了脱Me3Si基的产物(Me2SiSiMe2)[η-C5H4Fe(CO)]2(μ-CO)2(1)及1的热重排异构体[Me2SiC5H4-Fe(CO)2]2(2).将5的二甲苯溶液加热回流18h,则转化为其异构体[Me2Si(Me3SiC5H3)Fe(CO)2]2(6).脱硅基发生在由相应反应物制备5的过程中。且脱硅基是与反应物中(Me2SiSiMe2)桥的存在有关。5的晶体结构经X射线衍射测定属单斜晶系,P21/m空间群,晶体学数据:a=0.6780(1)nm,b=2.2303(9)nm,c=0.9988(1)nn,;β=98.96(1)°,V=1.4960nm3.Z=2,Dc=1.36g/cm3.     

1,2-二(对-甲苯基)-1,2-二甲基二硅桥连二环戊二烯基四羰基二铁的合成及热重排反应

Cl2MeSiSiMeCl2与环戊二烯基锂及对甲苯基溴化镁反应, 生成C5H5(p-Tol)MeSiSiMe(p-Tol)C5H5. 后者再与五羰基铁反应, 得到标题化合物[η5, η5-C5H4(p-Tol)MeSiSiMe(p-Tol)C5H4]Fe2(CO)2(μ-CO)2(3); 同时还得到两个单硅桥连副产物[η5, η5-(p-Tol)2MeSiSiMe(C5H4)2]Fe2(CO)2(μ-CO)2(4)和[η5, η5-(p-Tol)Me2SiSiMe(C5H4)2]Fe2(CO)2(μ-CO)2(5). 化合物3中顺式异构体(3a)占绝对优势, 可通过简单重结晶分离出纯品. 化合物3a在加热条件下发生分子内的硅硅键和铁铁键之间的复分解重排反应, 生成[η5-(p-Tol)MeSiC5H4Fe(CO)2]2(6). 该产物为顺反异构体的混合物(顺反异构体的摩尔比为4:3), 表明重排反应不涉及协同历程. 利用X射线衍射法测定了化合物4的分子结构.     

Benzofuran derivatives. Part 3 On the reactivities of the intermediates in benzofuran synthesis

3-Methyl-5-nitrobenzofuran ( 2 ) and 3-methyl-5-nitrobenzofuran-2-carboxylic acid ( 3 ) were obtained by heating 2-acetyl-4-nitrophenoxyacetic acid ( 1 ) with various bases in acetic anhydride. It appeared that 3-hydroxy-3-methyl-5-nitro-2,3-dihydrobenzofuran-2-carboxylic acid ( 4 ) was the intermediate in the benzofuran synthesis. The properties of 4 were examined under various conditions. Using strong bases such as triethyl-amine in place of sodium acetate, 3-methyl-5-nitrobenzofuran-2-carboxylic acid ( 3 ) was obtained exclusively. However, in the presence of acetic acid in the reaction mixture 3-methyl-5-nitrobenzofuran ( 2 ) was obtained in good yield. The reaction pathways for the formation of 2 and 3 are discussed.     

Synthesis and Characterization of the Chiral Skeleton Cluster [NiRuMo(CO)_5(μ_3-S)(η~5-C_5H_5)(η~5-C_5H_4COCH_3)]

1 INTRODUCTION The chemistry of transition metal cluster has enjoyed an exceptional growth since the mid 1970s[1, 2], especially in recent years the structural and bonding aspects of mixed-metal tetrahedral skeleton clusters have been extensively studied[3]. One important reason is that such chiral cluster can induce an asymmetric catalysis potentially. In our research group, considerable efforts have been directed to the synthesis of chiral tetrahedral clusters containing four different…     

新型苯并二氢呋喃合二酮酸类化合物的合成及其与整合酶分子对接研究

以阿魏酸甲酯为原料,通过氧化偶联构建2-芳基苯并二氢呋喃骨架,再经傅克酰基化和酯缩合反应依次制得(E)-3-［2-(4-羟基-3-甲氧基-5-乙酰基)苯基-3-甲氧羰基-7-甲氧基-2,3-二氢苯［b］并呋喃-5-基］丙烯酸甲酯（3）和(E)-3-［2-(4-羟基-3-甲氧基-5-甲氧羰基乙酰基)苯基-3-甲氧羰基-7-甲氧基-2,3二氢苯并［b］呋喃-5-基］丙烯酸甲酯（4）; 4经水解反应合成3-【2-羟基-3-甲氧基-5-｛5-［2-（甲氧基羰基）乙烯基］-7-甲氧基-3-甲氧羰基-2,3-二氢苯并［b］呋喃-2-｝基】苯基-3-氧丙酸（5）,化合物3~5未见文献报道,其结构经¹H NMR, ¹³C NMR和MS(ESI)表征。采用分子对接软件Autodock vina对化合物2~5与HIV-1整合酶核心部位高度同源的PFV IN（PDB: 3L2V）进行对接,计算结果显示该类化合物能与整合酶形成稳定的复合物,具有1,3-二酮基团的化合物3, 4和5能与整合酶中金属离子产生螯合作用,其中化合物5的结合作用最强。     

间氯苯基锰卟啉-5-氟尿嘧啶配合物的合成及其对癌细胞的抑制活性

合成了4种新5-氟尿嘧啶-卟啉衍生物：5-[3-(2-(5-氟尿嘧啶-1-基)乙氧基)苯基]-10,15,20-三(3-氯苯基)卟啉(1a)、5-[3-(2-(5-氟尿嘧啶-1-基)乙氧基)苯基]- 10,15,20-三(3-氯苯基)锰卟啉(2a)、5-[3-(3-(5-氟尿嘧啶-1-基)丙氧基)苯基]-10,15,20-三(3-氯苯基)锰卟啉(2b)和5-[3-(4-(5-氟尿嘧啶-1-基)丁氧基)苯基]-10,15,20-三(3-氯苯基)锰卟啉(2c),通过UV-Vis、IR、MS及元素分析表征了它们的结构。 用噻唑蓝法（MTT法）测定了化合物2a、2b和2c对人胃癌细胞株BGC-823的抑制活性。 化合物2b的半数抑制浓度IC50为1.34 μmol/L,表明有一定的细胞毒作用。     

Reaction of 3-acetonyl-5-cyano-1,2,4-thiadiazole with phenylhydrazine hydrochlorides: indolization and phenylpyrazolation

Treatment of 3-acetonyl-5-cyano-1,2,4-thiadiazole (1) with 4-methyl or 4-methoxyphenylhydrazine hydrochloride provided 5-cyano-3-(2,5-dimethylindol-3-yl)-1,2,4-thiadiazole (2) or 5-cyano-3-(5-methoxy-2-methylindol-3-yl)-1,2,4-thiadiazole (3) as the sole product, respectively. In contrast, treatment of 1 with phenylhydrazine hydrochloride resulted in the formation of 5-cyano-3-(2-methylindol-3-yl)-1,2,4-thiadiazole (4) and the unexpected 5-cyano-3-(3,5-dimethyl-1-phenylpyrazol-4-yl)-1,2,4-thiadiazole (5). In a similar manner, when 1 was treated with 4-chlorophenylhydrazine hydrochloride, indolization was suppressed by phenylpyrazolation giving rise to 5-cyano-3-(5-chloro-2-methylindol-3-yl)-1,2,4-thiadiazole (6) and 5-cyano-3-[1-(4-chlorophenyl)-3,5-dimethylpyrazol-4-yl]-1,2,4-thia diazole (7). The reaction mechanism is discussed. Compounds 4, 5 and 6 exhibited weak antimicrobial activity against Helicobacter pylori.