四溴-2,3-萘酞菁铅的合成及性质研究

以1,8-二氮杂双环[5.4.0]+-碳烯-7(DBU)为催化剂合成了中心原子为重原子铅、环取代基为重原子溴的萘酞菁配合物四溴-2,3-萘酞菁铅[PbNcBr₄],并研究了该配合物的电子吸收光谱、热稳定性、光限幅特性及重原子对其光限幅特性的影响及其机理.该配合物在近红外区(795～825nm)有强吸收(Q带),溴取代可使配合物Q带略微蓝移,溶剂的极性对配合物的电子吸收光谱有较大影响.该配合物具有较高的热稳定性,气氛对其热稳定性有明显影响,其在N₂气氛中的热稳定性明显比在O₂气氛中的高;在O₂气氛中为一步分解,在N₂气氛中为多步分解.标题配合物具有优异的非线性光限幅特性,在高线性透射率88%时的限幅阈值为148mJ/cm²,限幅幅值为332mJ/cm²,损伤阈值约为3J/cm²,其光限幅特性明显优于光限幅新材料C₆₀(透射率70%时,限幅阈值大于240mJ/cm²).重原子铅和溴可显著优化材料的非线性光限幅特性.     

含两个酰胺基团的卟啉二聚体分子间氢键引起的发光光谱红移

通过5-（4-甲酸基苯基）-10,15,20-三（4-十二烷氧基苯基）卟啉（HAcTPP）与乙二胺,丙二胺和丁二胺反应,制备了一类含2个酰胺基团的卟啉二聚体C₂（AmTPP）₂、C₃（AmTPP）₂和C₄（AmTPP）₂以及相应的配合物Pt2C₂（AmTPP）₂、Pt2C₃（AmTPP）₂和Pt2C₄（AmTPP）₂。采用¹H NMR、¹³C NMR、质谱、元素分析、循环伏安、紫外-可见吸收光谱和荧光发射光谱等对二聚体的化学结构、热稳定性、电化学和光物理性质进行了表征。实验发现,二聚体和相应的铂配合物的光致发光（PL）光谱性质与溶液的浓度有关,在10^-7 mol·L^-1 THF稀溶液中,二聚体与单羧基卟啉的PL光谱基本一致。当浓度增加到10^-3 mol·L^-1 THF溶液时,二聚体的光致发光光谱最大值从657 nm红移到675 nm,比单羧基卟啉红移了18 nm。当与金属铂配位后,这种发射光谱随浓度增加而变化的特性更加明显。二聚体配合物在10^-7 mol·L^-1 THF稀溶液中PL光谱就产生了红移现象,最大发射峰λ_max为673 nm,比单羧基卟啉红移16 nm。在高浓度10^-4 mol·L^-1 THF溶液和升华薄膜中的PL最大发射峰进一步红移到727 nm的近红外区。进一步,为了证实二聚体配合物分子间的π-π和Pt-Pt相互作用,我们以配合物Pt2C₃（AmTPP）₂为例,对二聚体配合物固体在常温和低温77 K的PL光谱进行了测试,发现固体配合物表现出与温度相关的PL性质。当温度降到77 K时,配合物的最大发射峰从658 nm红移到674 nm,红移了16 nm。实验表明,卟啉二聚体和相应的配合物的红移现象与二聚体的分子结构直接相关,卟啉二聚体中的两个酰胺基团能够产生较强的分子间氢键,导致二聚体分子之间产生一定程度的π-π和Pt-Pt相互作用,使得二聚体PL光谱产生红移。     

以2,3-二苯基吡嗪或2,3-二苯基喹喔啉为配体的单核和双核金属铂配合物的晶体结构与光物理性质

以2,3-二苯基吡嗪（H₂dpp）、5-甲基-2,3-二苯基吡嗪（H₂mdpp）和2,3-二苯基喹喔啉（H₂dpq）为配体,乙酰丙酮（Hacac）为辅助配体,合成了一类单核和双核金属铂配合物[Pt（Hdpp）（acac）]（1）、[Pt₂（dpp）（acac）₂]（2）、[Pt（Hmdpp）（acac）]（3）和[Pt（Hdpq）（acac）]（4）,并且得到了配合物2、3和4的晶体结构数据。通过对单核配合物1的类似物配合物3和双核配合物2的配位平面、分子扭曲程度等的晶体结构分析,我们合理地推断以2,3-二苯基吡嗪为配体的双核配合物2具有比相应的单核配合物1更加扭曲的分子平面。通过对配合物1和2的紫外-可见吸收光谱和激发光谱的比较,发现由于双核配合物2在激发态的构型变化造成了激发光谱中最低能带比相应的最低能量吸收带光谱红移了18 nm。因此,尽管双核配合物2具有与单核配合物1类似的紫外-可见吸收光谱,最低能吸收带仅比单核配合物1红移5 nm,但是双核配合物2的最大发射峰值λ_max为609 nm,比单核配合物1（λ_max=546 nm）红移了63 nm。双核配合物2的发射光谱红移现象与配合物的分子构型直接相关。分子扭曲程度更大的双核配合物2在激发态可能发生了一个向平面性更好的构型转变过程,从而进一步降低了激发态能量,造成了发射光谱的红移。     

大环金属铜(II)、镍(II)配合物的模板合成与晶体结构

用模板法合成了1个大环金属铜(II)配合物[CuLCl₂]·3H₂O (1)和3个大环金属镍(II)配合物[NiLCl₂] (2)，[NiL](ClO₄)₂ (3)和[NiLH₂](ClO₄)₄ (4)(L=3,10-二乙基-1，3，5，8，10，12-六氮杂十四烷)，通过X-射线衍射单晶结构分析测定了它们的晶体结构。晶体结构显示：配合物1和2的金属离子与大环配体的4个氮原子及大环平面轴向的2个氯离子以八面体配位方式配位；配合物3和4的金属离子与大环配体的4个氮原子以平面正方形配位方式配位，配合物4的侧链氮原子的质子化导致侧链结构翻转，使得其侧链与大环平面共面。     

联吡啶钌(Ⅱ)配合物的合成、晶体结构及其在染料敏化太阳能电池中的应用

制备了一个多吡啶钌(Ⅱ)配合物[Ru(bipy)₂(Pyap)](PF₆)₂ (1)(bipy=2，2′-联吡啶，Pyap=4-(2-吡啶亚甲氨基)-苯酚)，研究了它在染料敏化太阳能电池中的应用，对它进行了元素分析、IR、 ¹H NMR、UV-Vis、PL、XRD、CV、IV等表征。将配合物1的水溶液自然蒸发，得到配合物[Ru(bipy)₂(Pyap)](PF₆)₂·H₂O (2)的晶体，我们测定了它的单晶结构，配合物2的晶体属单斜晶系，P2₁/c空间群。配合物1的乙腈溶液在410～490 nm处有较宽的对应于MLCT跃迁的紫外吸收峰。在波长为400 nm光的激发下，分别在436、463、490 nm处各出现了1个荧光发射峰。其CV曲线表明1有2对可逆的氧化还原峰，在-0.158 V处有1个不可逆的氧化峰。用配合物1作为光敏染料组装成电池，测得最大输出功率P_max为0.025 mW，短路电流I_sc为0.142 mA，开路电压V_oc为402 mV，填充因子ff为0.444，光电转化效率η为0.025%。     

双脂肪胺钌卟啉的合成、结构表征和晶体结构

本文讨论了一系列双脂肪胺钌卟啉配合物，包括Ru(^Ⅱ)(Por)(H₂NR)₂和Ru(^Ⅱ)(Por)(HNR₂)₂［Por=四苯基卟啉(TPP)，中位-四(对甲苯基)卟啉(TTP)，中位-四(对氯苯基)卟啉(4-Cl-TPP);R=叔丁基，异丙基，环己基，正辛基，正十二烷基，R′=甲基和乙基］的合成，结构表征和晶体结构测定。钌羰基卟啉与间-氯过苯甲酸的反应混合物用过量的脂肪胺处     

希土离子不对称双氮杂冠醚配合物的合成、表征及CD谱

在乙醇中合成出三个希土硝酸盐与冠醚(+)-12,17-二乙基-1,4,7,10-四氧杂-13,16-二氮杂环十八烷(L)的配合物。经元素分析确定其组成为［Ln(NO₃)₂·L(+)］NO₃(Ln=La, Pr, Nd)。通过UV-VIS和FI-IR、电导测定等方法研究了配合物的配位结构和性质。测定并讨论了手性配合物［Pr(NO₃)₂·L(+)］NO₃的CD谱。     

含吩噻嗪金属配合物的合成及非线性光学性质研究

本文报道了一种新的配体:10-乙基-3-甲酰吩噻嗪缩肼基二硫代甲酸甲酯(HL)及其金属配合物的合成。采用了元素分析、质谱、核磁共振、红外光谱对配体及其金属配合物进行了表征。此外,并应用紫外、荧光和Z-扫描技术,测定了配体及其金属配合物的荧光最佳发射波长(λ_max^em)、荧光量子产率(Φ_f)、寿命(τ)和非线性光学性质。结果表明它们在DMF溶液中都能发射出较强的橄榄色荧光,配体及其金属配合物都有双光子吸收,并且金属配合物的非线性光学效应比配体明显增强。用半经验量子化学方法(RHF/PM3)计算结果与实验值较为吻合。     

(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷与镧系硝酸盐、硫氰酸盐配合物的合成表征和CD谱

合成了共15个未见文献报道的三价镧系离子与手性氮杂冠醚(+)-12-乙基-1，4，7，10-四氧杂-13-氮杂环十五烷(以下以L(+)表示)的配合物Ln(NO₃)₃·L(+)·H₂O(Ln=La、Ce、Pr、Nd); Ln(SCN)₃·L(+)·H₂O(Ln=La、Pr、Nd、Sm、Eu、Gd-Er、Yb)。对所合成配合物进行了元素分析、电导、红外、可见吸收光谱、比旋光度和圆二色谱(CD谱)的测试，并对配合物的有关物理化学性质进行了讨论。     

四乙酰哌嗪苯氧基酞菁锌及其蛋白质复合物的制备、表征与光动力活性

合成了2个酞菁锌配合物，即α-四(4-(4-乙酰哌嗪)苯氧基))酞菁锌(C₈₀H₇₂N₁₆O₈Zn) (1)和β-四(4-(4-乙酰哌嗪)苯氧基)酞菁锌(C₈₀H₇₂N₁₆O₈Zn) (2)，并通过¹H NMR，MS，IR和元素分析等手段进行表征。配合物1、2在N，N-二甲基甲酰胺、四氢呋喃和正辛醇等有机溶剂中呈现出典型的酞菁的单体吸收光谱特征，Q带分别位于693~698 nm和681~682 nm，相对于β位取代者，α位取代的配合物的Q带明显红移。在含水溶剂中的吸收光谱测试显示，α位取代较β位取代更能有效地阻止配合物在含水溶剂中形成聚集体。通过吸收光谱和荧光光谱研究了2个配合物与血清白蛋白(BSA，HSA)和转铁蛋白(apoTf)的相互作用，结果表明，结合常数在(1~20) × 10⁵ mol^-1·L之间，相对而言， β位取代的配合物与白蛋白的结合能力强于α位取代者。同时，制备了1-BSA、2-BSA、1-HSA、1-apoTf和1-FeTf等非共价键结合的酞菁-蛋白质复合物。对MCF-7乳腺癌细胞的光动力杀伤作用的测试初步表明，复合物的活性较高，活性顺序为：1-BSA > 1-FeTf > 1-HSA，1-apoTf > 2-BSA > 1 > 2。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.