五元杂环spacer结构调控的分子内电荷交互作用

研究五元杂环(spacer)桥对分子内电荷传递调控规律是开发功能分子材料的基础。本文通过环合反应制备了9个2,5-双二茂铁基五元杂环衍生物,包括: 2,5-双二茂铁基-1-苯基-吡咯(1),2,5-双二茂铁基呋喃(2),2,5-双二茂铁基噻吩(3),2,5-双二茂铁基-1H-咪唑(4),2,5-双二茂铁基噁唑(5),2,5-双二茂铁基噻唑(6),2,5-双二茂铁基-1H-1,3,4-三氮唑(7),2,5-双二茂铁基-1,3,4-噁二唑(8)和2,5-双二茂铁基-1,3,4-噻二唑(9)作为模型分子。通过元素分析,傅里叶变换红外(FTIR)光谱,质谱(MS)和核磁共振(NMR)等手段对化合物结构进行了表征,采用循环伏安电化学(CV)和密度泛函(DFT)量化模拟计算研究了分子内电荷传递与五元杂环(spacer)结构间的调控关系,发现化合物(1-9)二茂铁间电荷交互作用随着spacer中杂原子数量的增加而减小,分子内电荷选择短程杂原子桥作为传输通道,spacer结构对二茂铁间电荷传递发挥着重要的调控作用。     

氟取代噻咯衍生物结构和光电性能的理论研究

采用密度泛函理论在B3LYP/6-31G(d)水平上计算了1,1-二甲基-2,3,4,5-四苯基噻咯(PSP)及其8种氟取代衍生物的几何结构与光电性质. 计算结果表明, 2,5位苯基上氟取代对PSP结构和光电性质的影响主要由氟原子的取代位置决定, 而取代基个数的增加能加强相关影响. 苯基上邻对位氟取代对分子构型影响较大, 导致HOMO-LUMO能隙增大, 光谱显著蓝移; 而间位氟取代显示诱导作用突出, 使2,5位侧链吸电子能力增强, 同时LUMO能级降低, 电子亲和势增大更有利于电子的注入.     

新型单羟基氯代咔咯的合成及其光断裂DNA性质

以五氟苯甲醛和吡咯经缩合反应合成了五氟苯基二吡咯烷烃(1);1与3-氯-4-羟基苯甲醛经缩合反应合成了一个新的10-位苯环被氯原子取代的单羟基自由咔咯——10-(3-氯-4-羟苯基)-5,15-二(五氟苯基)咔咯(2),收率12.0%,其结构经UV-Vis,1H NMR,19F NMR,HR-ESI-MS和X-射线单晶衍射表征。琼脂糖凝胶电泳实验发现:2在光照下能够有效引起超螺旋质粒p BR 322 DNA发生断裂,当浓度为100μmol·L-1时,活性最强,断裂百分比为68%。     

苯基吡咯类杀菌剂的设计合成及三维-定量构效关系(3D-QSAR)研究

为寻找新型吡咯类农药,基于杀菌剂氟咯菌腈设计合成了21个苯基吡咯类化合物,在吡咯环上引入甲基基团,其目的是探究N位取代基对该类化合物活性的影响.通过1H NMR、FTIR、单晶X射线衍射、高分辨质谱、元素分析和熔点测定等对目标化合物结构进行了表征与确认,并通过挥发法培养得到16个目标化合物的单晶结构.5种病原菌抑菌活性测试结果显示:在10mg/L浓度条件下,4-(2-氯苯基)-1H-吡咯-3-腈(4b),4-(2-溴苯基)-1H-吡咯-3-腈(4c),4-(2-(三氟甲基)苯基)-1H-吡咯-3-腈(4d), 4-(2-氯-3-氟苯基)-1H-吡咯-3-腈(4g), 4-(2,3-二氯苯基)-1H-吡咯-3-腈(4h)对4种病菌表现出较好甚至高于阳性对照的抑菌效果,其中化合物4g在1 mg/L浓度条件下对3种病菌的抑制效果仍达到80%以上,而氮位甲基取代的目标化合物对水稻纹枯病菌表现出专一的抑菌活性.为了开发出更有效的抗水稻纹枯病菌化合物,采用比较分子力场分析(Co MFA)方法对20个化合物的水稻纹枯病菌活性进行初步的三维-定量构效关系(3D-QSAR)研究,建立了一个有效的Co MFA模型(q~2=0.503, r2=0.974),展现了良好的预测能力,为后续该系列化合物的进一步优化提供了理论支持.     

新型吡咯类衍生物的合成

2,5-己二酮和胺(氨基硫脲、硫脲、苯胺、氨基酸)经过Paal-Knorr反应合成6个2,5-二甲基-N-取代吡咯衍生物;分别以新合成的N-吡咯甘氨酸、N-苯基吡咯化合物为原料,进行酯化反应和Mannich,Friedel-Craft反应,合成3个N-(2,5-二甲基吡咯)甘氨酸酯类化合物和2个N-苯基-2,5-二甲基吡咯衍生物.所有化合物都通过IR,1HNMR,13CNMR,HRMS波谱方法对其结构进行了确证.     

新型2，6-双（3，5-二取代吡唑基-1-羰基）吡啶的合成

报道了四种吡唑衍生物和它们四种新型的杂环酰胺衍生物的合成，它们是3，5-二甲基吡唑(1)，5-甲基-3-苯基吡唑(2)，3，5-二苯基吡唑(3)，5-甲基-3-二茂铁基吡唑(4)，2，6-双(3，5-二甲基吡唑基-1-羰基)吡啶(5)，2，6-双(5-甲基-3-苯基吡唑基-1-羰基)吡啶(6)，2，6-双(3，5-二苯基吡唑基-1-羰基)吡啶(7)和2，6-双(5-甲基-3-二茂铁基吡唑基-1-羰基)吡啶(8)．并对它们进行了元素分析，FT-IR，^1H NMR和^13C NMR等波谱分析．     

对称4-枝和8-枝噁二唑衍生物的合成与荧光性质

采用Wittig-Horner和Heck反应合成了3个对称多枝[1,3,4]-噁二唑衍生物2,5-双{4-{4-[N,N-二(4-溴苯基)-氨基] 苯乙烯基}苯基}-1,3,4-噁二唑(BrPASPO), 2,5-双{4-{4-{N,N-二{4-{4-[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2-]苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(TPASPO)和2,5-双{4-{4-{N,N-二{4-{3,5-二[5-(4-叔丁基苯基)-1,3,4-噁二唑基-2]-苯乙烯基}苯基}氨基}苯乙烯基}苯基}-1,3,4-噁二唑(OPASPO). 目标化合物的结构经过红外光谱、核磁共振氢谱、质谱和熔点确认. 在CH2Cl2溶液中三者的最大吸收波长分别在403 (BrPASPO), 408 (TPASPO)和409 nm (OPASPO), 荧光发射峰分别为495 (BrPASPO), 509 (TPASPO)和506 nm (OPASPO). 化合物TPASPO和OPASPO在CH2Cl2溶液中的荧光量子产率分别为0.47和0.45. 8枝化合物的荧光寿命高于4枝化合物. 对称多枝化合物具有很强的分子内电荷转移能力和荧光发射能力.     

1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑盐的合成、晶体结构及性质研究

以二茂铁甲醛为原料,在对甲苯磺酸催化下,与邻苯二胺缩合得到1-二茂铁基甲基-2-二茂铁基苯并咪唑(2),化合物2与碘代烷进行烷基化反应得到1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑碘盐(3,4),并通过阴离子交换反应得到1-二茂铁基甲基-2-二茂铁基-3-烷基苯并咪唑六氟磷酸盐(5,6)及双三氟甲磺酰亚胺盐(7,8).利用1H NMR,13C NMR,IR,MS,HRMS及元素分析对所有产物进行结构表征.化合物5的单晶结构表明该化合物通过分子间氢键作用自组装成了沿c轴无限延伸的一条链状超分子结构.电化学分析表明化合物3～8中的Fe1与Fe2由原来的一组氧化还原峰分离成了两组氧化还原峰.UV-Vis吸收光谱曲线表明所有产物具有光致电荷迁移现象.DSC-TG(差示扫描量热-热重)曲线显示所得碘盐化合物对高氯酸铵(AP)热分解有较好的催化效果.     

1-苯基-4-取代酞嗪衍生物合成及抗肿瘤活性评价（英文）

为了找到更有效和更经济的抗肿瘤药物,合成了一系列1-苯基-4-取代酞嗪衍生物,并评估了其体外抗增殖活性.所合成的化合物的结构都通过~1 H NMR,~(13) C NMR和HRMS确证.并且通过3-(4,5-二甲基噻唑-2)-2,5-二苯基四氮唑溴盐(MTT)法评估了目标化合物对四种人类癌细胞株的抗肿瘤活性.结果表明:一些化合物具有良好的抗肿瘤活性,特别是N-(4-甲氧基苯基)-2-((4-苯基酞嗪-1-基)硫基)乙酰胺(5f)和N-(3-氯-4-氟苯基)-2-(4-(4-苯基酞嗪-1-基)哌嗪-1-基)乙酰胺(8c)表现出了更好的抗肿瘤活性,对人类食管癌细胞的活性优于5-氟尿嘧啶.IC50值分别为8.13和9.31μmol·L~(-1).     

新型N~6-哌嗪取代腺苷衍生物的合成及其抗肿瘤活性

以腺苷为母体,对其N6-位进行结构改造,首先经邻位双羟基保护,N6-位氯代,再在N6-位引入哌嗪环制得中间体2',3'-异丙叉-6-哌嗪嘌呤核苷(4);4与N-氯乙酰苯胺类似物(6a~6h)偶联后脱除邻位双羟基保护合成了8个新型的N6-哌嗪取代腺苷衍生物(8a~8h),其结构经1H NMR,13C NMR和HR-ESI-MS表征。采用MTT法研究了8a~8h对Hela肿瘤细胞的抑制活性。结果表明:大部分目标化合物对Hela肿瘤细胞具有较好的抑制活性,其中2-{4-[9-(3,4-二羟基-5-羟甲基-四氢呋喃-2-基)-9H-嘌呤-6-基]-哌嗪-1-基}-N-(3-氟苯基)-乙酰胺(8e)的活性最好,IC50为21.74μmol·L-1。     

NMR Investigation of beta-Substituted High-Spin and Low-Spin Iron(III) Tetraphenylporphyrins

The NMR spectra of a series of beta-substituted iron(III) tetraphenylporphyrin (2-X-TPP) complexes have been studied to elucidate the relationship between the electron donating/withdrawing properties of the 2-substituent and the (1)H NMR spectral pattern. The electronic nature of the substituent has been significantly varied and covered the -0.6 to 0.8 Hammett constant range. Both high-spin and low-spin complexes of the general formula (2-X-TPP)Fe(III)Cl and [(2-X-TPP)Fe(III)(CN)(2)](-) have been investigated. The (1)H NMR data for the following substituents (X) have been reported: py(+), NO(2), CN, CH(3), BzO (C(6)H(5)COO), H, D, Br, Cl, CH(3), NH(2), NH(3)(+), NHCH(3), OH, and O(-). The (1)H NMR resonances for low-spin dicyano complexes have been completely assigned by a combination of two-dimensional COSY and NOESY experiments. In the case of selected high-spin complexes, the 3-H resonance has been identified by the selective deuteration of all but the 3-H position. The pattern of unambiguously assigned seven pyrrole resonances reflects the asymmetry imposed by 2-substitution and has been used as an unique (1)H NMR spectroscopic probe to map the spin density distribution. The pyrrole isotropic shifts of [(2-X-TPP)Fe(III)(CN)(2)](-) are dominated by the contact term. In order to quantify the substituent effect, the dependence of isotropic shift of all low-spin pyrrole resonances and 3-H high-spin pyrrole resonance versus Hammett constants has been studied. The electronic effect is strongly localized at the beta-substituted pyrrole. The major change of the isotropic shift has also been noted for only one of two adjacent pyrrole rings, i.e., at 7-H and 8-H positions. These neighboring protons, located on a single pyrrole ring, experienced opposite shift changes when electron withdrawing/donating properties were modified. Two other pyrrole rings for all investigated derivatives revealed considerably smaller, substituent related, isotropic shift changes. A long-range secondary isotopic shift has been observed for [(2-D-TPP)Fe(III)(CN)(2)](-). The effect is consistent with a general spin density distribution mechanism due to beta-substitution. A fairly good correlation between the 3-H isotropic shift of (2-X-TPP)Fe(III)Cl and the Hammett constant has been found as well. The observed contact shift pattern of [(2-X-TPP)Fe(III)(CN)(2)](-) reflects spin pi delocalization into the highest filled MO equivalent to the unsubstituted porphyrin 3e(pi) orbital. To account for the substituent contribution, the semiquantitative Fenske-Hall LCAO method has been used to determine the molecular orbitals involved in the spin density delocalization. For low-spin complexes, (13)C pyrrole resonances of carbons bearing a proton have been identified by means of a (1)H-(13)C HMQC experiment. The reversed order of (13)C resonance patterns as compared to their (1)H NMR counterparts has been determined, e.g., the largest isotropic shift of 3-H has been accompanied by the smallest measured (13)C isotropic shift. Analysis of the isotropic shifts in (2-X-TPP)Fe(III)Cl and [(2-X-TPP)Fe(III)(CN)(2)](-) suggests that the observed regularities of the electronic structure modification due to the beta-substitution should apply to iron(III) natural porphyrin or geoporphyrin complexes.     

Synthesis and characterization of electroactive ferrocene derivatives: ferrocenylimidazoquinazoline as a multichannel chemosensor selectively for Hg2+ and Pb2+ ions in an aqueous environment

The synthesis and characterization of ferrocene (Fc) derivatives 4-[2,5-diferrocenyl-4-(4-pyridyl)imidazolidin-1-ylmethyl]pyridine (1), ferrocenylmethylenepyridin-3-ylmethylamine (2), N,N'-bis(ferrocenylmethylene)-2,4,6-trimethylbenzene-1,3-diamine (3), and 6-ferrocenyl-5,6-dihydro[4,5]imidazo[1,2-c]quinazoline (4) have been described. Structures of 1, 2, and 4 have been determined by single-crystal X-ray diffraction analyses. At 25 °C, 1-3 are nonfluorescent, while 4 displays moderate fluorescence and chromogenic, fluorogenic, and electrochemical sensing selectively toward Hg(2+) and Pb(2+) ions. Association constants (K(a)) for Hg(2+) and Pb(2+) have been determined by the Benesi-Hildebrand method. Job's plot analysis supported 1:1 and 1:2 stoichiometries for Hg(2+) and Pb(2+) ions. Cyclic voltammograms of 1-4 exhibited reversible waves corresponding to a ferrocene/ferrocenium couple. The wave associated with 4 (+0.0263 V) exhibited positive (ΔE(pa) = 0.136 V) and negative (ΔE(pa) = 0.025 V) shifts in the presence of Hg(2+) and Pb(2+) ions, respectively. The mode of interaction between metal ions and 4 has been supported by (1)H NMR spectroscopy and mass spectrometry studies and verified by theoretical studies. It presents the first report dealing with ferrocene-substituted quinazoline as a multichannel chemosensor for Hg(2+)/Pb(2+) ions.     

Reductive allylation of pyrrole with allylboranes. Synthesis oftrans- andcis-2,5-disubstituted pyrrolidines

Pyrrole undergoes reductive mono- and diallylation on successive treatment with β,γ-unsaturated organoboron derivatives (triallylborane, allyl(dipropyl)borane, and triprenylborane) and alcohols to give 2-allylated 3-pyrrolines andtrans-2,5-diallylated pyrrolidines. The addition of both the first and second boron-allylic fragment to the heterocycle proceeds with rearrangement. A method for transformation of thetrans-2,5-diallylpyrrolidine into thecis-isomer (heating with triallylborane at 190 °C) was developed and a series ofN-substituted derivatives of these pyrrolidines was synthesized. A method for the preparative synthesis of nonsymmetrically substitutedtrans- andcis-2-alkyl(phenyl)-5-allylpyrrolidines, based on reductive allylboration of pyrrole followed by 1,2-addition of RLi to the 5-allyl-1-pyrroline that formed, was also developed. A direct confirmation of intermediate formation of 2H- and 3H-pyrrole tautomers under the action of allylboranes was obtained. The adduct of 2H-pyrrole with BF₃ was detected by NMR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1718–1728, September, 1999.     

多二茂铁基二氮杂己烷及其过渡金属配合物的合成

乙二胺与二茂铁甲醛或双二茂铁甲基氟硼酸盐反应，合成了１，６－二（二茂铁基）－２，５－二氮杂己烷和１，１，６，６－四（二茂铁基）－２，５－二氮己烷，它们与过渡金属（Ｆｅ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｃｕ＾２＋，Ｚｎ＾２＋）盐在乙醇或乙醇－二氯甲烷中反应，是１４种过渡金属配合物，对这些化合物进行了表征，二种配体及其铜配合物用作复合固体推进剂的燃速调节剂时，基本不迁移，而燃速催化效率均超过辛基二茂铁。     

The effect of acetyl on the electronic communication of carbon-bridged diferrocene

Diferrocenylmethane (1) and 2-acetyl(diferrocenyl)methane (2) were synthesized and characterized by elemental analysis, FT-IR, and NMR. The molecular structures of 1 and 2 were determined using X-ray single crystal diffraction. The effect of acetyl group on electronic communication between two ferrocenyl units of 2 was investigated through cyclic voltammetry and density functional theory calculation. The acetyl did not influence electronic communication between two ferrocenyl units. The key factor that effected electronic communication of carbon-bridged diferrocenyl derivatives was charge density of the bridged carbon.     

Influencing the electronic interaction in diferrocenyl-1-phenyl-1H-pyrroles

Functionalised diferrocenyl-1-phenyl-1H-pyrroles were synthesised using Negishi C,C cross-coupling reactions. The influence of different substituents at the phenyl moiety on the electronic interaction was studied using electrochemistry (cyclic and square-wave voltammetry) and spectro-electrochemistry (in situ UV/Vis-NIR spectroscopy). The ferrocenyl moieties gave rise to two sequential, reversible redox processes in each of the diferrocenyl-1-phenyl-1H-pyrroles. The observed ΔE(1/2) values (ΔE(1/2) = difference between first and second oxidation) range between 420 and 480 mV. A linear relationship between the Hammett constants σ of the substituents and the separation of the redox potentials exists. The NIR measurements confirm electronic communication between the iron centers as intervalence charge transfer (IVCT) absorptions were observed in the corresponding mixed-valent monocationic species. All compounds were classified as class II systems according to Robin and Day (M. B. Robin and P. Day, Adv. Inorg. Chem., 1967, 10, 247-423). The oscillator strength of the charge transfer transition highly depends on the electron donating or electron withdrawing character of the phenyl substituents. This enables direct tuning of the intermetallic communication by simple modification of the molecule's functional group. Hence, this series of molecules may be regarded as model compounds for single molecule transistors.     

Structures of a tetradentate ferrocenyl ligand and its oxorhenium(V) complex in solution and in the solid state

The novel ferrocenyl ligand rac-1,6-diferrocenyl-N,N'-bis(2-hydroxypropyl)-2,5-diazahexane (1, H(2)L) was synthesized from ferrocenylcarboxaldehyde and ethylenediamine followed by the reduction of the Schiff base with LiAlH(4) and subsequent N-alkylation with 1,2-propyleneoxide. The dianion of H(2)L reacted with [ReO(PPh(3))(2)Cl(3)], and the product was treated with NH(4)PF(6) to afford the complex [ReO(L-N(2)O(2))PPh(3)]PF(6) (2). Both the ferrocenyl ligand and the complex were characterized in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction studies. NMR investigations reveal two solvent-dependent isomers for the ferrocenyl ligand in solution of which the major form is the more ordered one. The cation of 2 displays a nonsymmetrically coordinated N(2)O(2) ligand.     

Strategies for electrooptic film fabrication. Influence of pyrrole-pyridine-based dibranched chromophore architecture on covalent self-assembly, thin-film microstructure, and nonlinear optical response

The new dibranched, heterocyclic "push-pull" chromophores bis{1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (1), 1-(pyrid-4-yl)-2-(N-methyl-5-formylpyrrol-2-yl)ethylene (2), {1-(N-methylpyridinium-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}{(1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane (3), N-methyl-2-[1-(N-methylpyrid-4-yl)ethen-2-yl]-5-[pyrid-4-yl]ethen-2-yl]pyrrole iodide (4), bis{1-(N-methyl-4-pyridinio)-2-[2-(N-methylpyrrol-5-yl)]ethane}methane iodide (5), and N-methyl-2,5-[1-(N-methylpyrid-4-yl)ethen-2-yl]pyrrole iodide (6) have been synthesized and characterized. The neutral (1 and 2) and monomethyl salts (3 and 4) undergo chemisorptive reaction with iodobenzyl-functionalized surfaces to afford chromophore monolayers SA-1/SA-2 and SA-3/SA-4, respectively. Molecular structures and other physicochemical properties have been defined by (1)H NMR, optical spectroscopy, and XRD. Thin-film characterization by a variety of techniques (optical spectroscopy, specular X-ray reflectivity, atomic force microscopy, X-ray photoelectron spectroscopy, and angle-dependent polarized second harmonic generation) underscore the importance of the chromophore molecular architecture as well as film growth method on film microstructure and optical/electrooptic response.     

N-substituted 2,5-Di(2-thienyl)pyrroles. Synthesis and electrochemical properties

2,5-Dithienylpyrroles containing p-substituted benzene ring at the nitrogen atom were synthesized. The formylation and subsequent crotonic condensation of N-(4-nitrophenyl)-2,5-di (2-thienyl)pyrrole was performed. Electrochemical behavior of the compounds and electrochromic properties of 2,5-di(2-thienyl)-pyrrole containing p-semidine fragment at its nitrogen atom were studied.