苯并咪唑衍生配体锌-铕(或铽)异金属双核配合物的合成、结构与光学性质

合成了四个锌-铕(或铽)异金属双核配合物[ZnLnL¹(NO₃)₃Py] (Ln=Eu (1), Tb (2); HL¹=1-H-2-(2-羟基-3-甲氧基苯基)苯并咪唑; Py=吡啶)和[ZnLnL²(NO₃)₃Py] (Ln=Eu (3), Tb (4); HL²=1-H-2-(2-羟基-3-甲氧基-5-溴苯基)苯并咪唑; Py=吡啶), 其中1、2、3是单晶态, 化合物4则为多晶样品; 通过单晶X射线衍射、元素分析、傅里叶变换红外光谱和电喷雾质谱对化合物进行了表征. 化合物的紫外-可见吸收光谱、荧光激发和发射光谱表明配体的激发态能量有效传递到配合物中的镧系金属离子中, 含有铽(III)离子的配合物发射出其特征发射光谱, 而含有铕(III)离子的配合物由于其它去活方式, 没有辐射出铕(III)离子的特征发射光谱.     

α-二亚胺钴配合物催化1,3-丁二烯高活性与高顺式-1,4选择性聚合

合成了一系列α-二亚胺钴配合物[ArN=C(Me)-(Me)C=NAr]CoCl₂(Ar=C₆H₅, 3a; 4-MeC₆H₄, 3b; 4-MeOC₆H₄, 3c; 4-FC₆H₄, 3d; 4-ClC₆H₄, 3e; 2-MeC₆H₄, 3f; 2-EtC₆H₄, 3g; 2-ⁱPrC₆H₄, 3h; 2,4,6-Me₃C₆H₂, 3i; 2,6-Et₂C₆H₃, 3j; 2,6-ⁱPrC₆H₃, 3k)和作为对比的吡啶双亚胺二氯化钴配合物(4a), 并用X射线单晶衍射方法研究了配合物3i, 3k和4a的分子结构. α-二亚胺钴配合物在倍半乙基氯化铝的作用下对丁二烯聚合有较高的催化活性,得到的顺式-1,4结构含量达98%,且有较高分子量(M_n≈1×10⁴-1×10⁵)的聚丁二烯. 配体的电子效应影响催化剂的活性及顺式-1,4选择性, 而配体的空间位阻对丁二烯聚合几乎没有影响. 详细研究了聚合时间、聚合温度、烷基铝助催化剂及铝比等条件对丁二烯聚合行为的影响.     

加替沙星与牛血清白蛋白结合作用的光谱学研究

通过荧光猝灭光谱研究了15℃和37℃下水溶液中加替沙星（HGA）与牛血清白蛋白(BSA)的结合作用。由Stern-Volmer曲线计算出双分子猝灭速率常数分别为：K_q=9.28×10¹²L·mol^－1·s^－1(15℃)，K_q=8.51×10¹²L·mol^-1·s^-1 (37 ℃)。结果显示，HGA对BSA的荧光猝灭机理是一种静态猝灭过程。本文获得的热力学参数表明HGA主要以静电引力与BSA结合。HGA的浓度与BSA的荧光强度之间关系的研究表明，HGA与BSA按1 ：1摩尔比结合，结合反应的平衡常数K₀= 6.80×10⁴ L·mol^－1。另外，通过Förster原理计算了HGA与BSA的结合距离及能量转移效率。     

4-硝基咪唑A-带激发态结构动力学

通过共振拉曼光谱实验和量子化学计算的方法研究了4-硝基咪唑(4NI)A-带激发态衰变动力学. 对4NI的振动光谱、紫外电子吸收光谱、荧光光谱和共振拉曼光谱进行了指认. 在全活化空间自洽场法(CASSCF)/6-31G(d)计算水平下获得了单重激发态S₁(n_Oπ^*)和S₂(ππ^*)和势能面交叉点S₁(n_Oπ^*)/S₂(ππ^*)的优化几何结构和能量, 分析了A-带共振拉曼光谱的强度模式特征, 获得了短时结构动力学, 并结合全活化空间自洽场法(CASSCF)理论计算结果确定了4NI 在S₂(ππ^*)态衰变通道主要是S_{2, FC}→S_{2, min}(ππ^*)→S₀辐射弛豫.     

一种含咔唑基团的混配型钌(II)配合物的合成、表征和酸碱性质研究

合成了钌(II)配合物cis-[Ru(HL)(Hdcbpy)(NCS)₂]^－•[N(C₄H₉)₄]^＋ (HL＝2-(9-乙基-9H-3-咔唑基)-1H-咪唑[4,5-f] [1,10]邻菲啰啉, H₂dcbpy＝4,4'-二羧酸-2,2'-联吡啶). 采用元素分析、核磁共振氢谱、红外光谱、紫外-可见吸收光谱、质谱(MS)对配合物进行了表征. 通过紫外-可见吸收光谱和稳态荧光光谱, 研究了该配合物的基态和激发态酸碱性质. 结果表明该配合物在基态时能发生5步质子化/去质子化反应, 表现出基于光致发光强度和激发态能量转移途径的质子化/去质子化诱导的分子开关性质.     

系列Ln(Ⅲ)配位聚合物的合成、结构及光物理性能(Ln(Ⅲ)=Yb、Ho、Er)

采用水热方法合成了3个Ln(Ⅲ)配位聚合物：[Ln(NH₂-C₆H₄-COO)₂DMF(HCOO)(H₂O)]_n(Ln=Yb 1,Ho 2,Er 3);通过X-单晶衍射、红外光谱(IR)、紫外吸收光谱(UV-Vis-NIR)、发射光谱(紫外可见荧光光谱和近红外发射光谱)等方法对化合物进行了表征。结果表明,化合物1、     

以吡啶为配体的镍配合物[Ni(py)3(H2O)3] (1, 5-nds)的合成、晶体结构及性质研究

采用缓慢蒸发法, 在水溶剂中合成了含氮配体单核Ni(Ⅱ)配合物[Ni(py)₃(H₂O)₃] (1, 5-nds)(py=pyridine, 1, 5-nds=1, 5-萘二磺酸根离子)。采用X射线单晶衍射、红外光谱、热分析和紫外可见光谱等方法对配合物进行了表征。X射线单晶衍射表征结果表 明, 该配合物晶体属于单斜晶系, 空间群为C2/c。晶体学参数:a=1.569 46(17) nm, b=1.219 95(12) nm, c=1.454 71(16) nm, β=14.547 1(16)°, V=2.765 1(5) nm³, Z=4。考察了该配合物的磁性和荧光性质。     

Mn(II)配合物的晶体结构及表面光电性能

采用水热法合成3个新的Mn(II)配合物[Mn(SO₄)(H₂O)₃]_n (1), [Mn2.5(HPO₄)(PO₄)(H₂O)₂]_n (2), [Mn(phen)₂(H₂O)₂]·(C₄H₄O₄)·4H₂O (3) (phen=1,10-邻二氮杂菲). 用X射线单晶衍射、表面光电压光谱(SPS)、红外光谱(IR)、紫外-可见吸收光谱(UV-Vis)、电子顺磁共振谱(EPR)对配合物进行了表征. 结构解析表明: 配合物1是具有2D结构的配合物, 氢键将其连接成3D超分子; 配合物2是具有3D无限结构的配合物; 配合物3是单核配合物, 再由多种氢键连接, 形成3D超分子. SPS结果表明, 3个配合物在300-800 nm范围内都呈现明显的光伏响应, 表明它们均具有一定的光-电转换性能. 讨论了配合物结构, 空间维度和中心金属离子配位环境的不同对配合物表面光电性能的影响以及SPS与UV-Vis的关联: 配合物的结构维度越高、规则性越好, SPS响应强度越大; 中心金属离子的直接配位原子种类的不同、所处外晶场的强弱不同, SPS响应带的数目和位置明显不同.     

基于1H-苯并咪唑-2-羧酸的三个镧系超分子化合物的结构、热分解动力学和荧光性质

在水热条件下合成了三个镧系超分子化合物[Ln(HBIC)₃]_n [Ln=Sm (1), Ho (2), Yb (3); H₂BIC=1H-苯并咪唑-2-羧酸], 其中化合物1、2呈单晶态, 化合物3则为粉末样品; 借助单晶X射线衍射(XRD)、粉末衍射、元素分析、红外(IR)光谱、热分析等手段对化合物进行了表征. 结构分析表明, 1-3为同构化合物, 都呈现二维的平面结构, 其中每一个镧系金属中心与来自五个HBIC^-配体的三个氮原子和五个氧原子以两种新的配位模式配位形成一个轻微扭曲的双帽三棱柱几何构型, 相邻的二维(2D)平面进一步通过强的氢键作用形成了一个三维(3D)的超分子结构. 热重分析结果表明, 化合物1-3在360 ℃前均保持稳定, 呈现出良好的热稳定性. 基于Kissinger和Ozawa-Doyle两种方法, 通过差示扫描量热(DSC)技术研究得到了化合物1热分解的动力学参数(指前因子A_K=1.286×10⁸ s^-1; 活化能E_K=199.3 kJ·mol^-1, E_O=205.2 kJ·mol^-1). 另外, 也研究了室温下化合物1和3的固态发光性能, 结果表明, 化合物1和3分别在可见光区和近红外光区呈现出相应镧系金属离子的特征发射.     

二氧化锰纳米颗粒调控的紫外可见吸收-荧光双通道传感器的构建及D-青霉胺的检测

以聚乙烯亚胺(PEI)同时作为模板和还原剂,基于原位氧化还原反应,一步法制备二氧化锰纳米颗粒(MnO₂ NPs),并对其形貌、组成、紫外可见吸收、催化氧化特性进行了表征。结果表明,MnO₂ NPs能够催化氧化邻苯二胺(OPD)为2,3-二氨基吩嗪(DAP),产生420 nm处的紫外可见吸收和560 nm处的荧光发射。D-青霉胺(DPA)中的活性巯基可与MnO₂发生特异性反应,还原降解催化剂,抑制其催化氧化活性,使得体系紫外可见吸收-荧光信号减弱甚至消失。基于DPA浓度与体系光谱信号变化的关系,我们建立了MnO₂ NPs介导的紫外可见吸收-荧光双通道传感DPA的新方法。荧光传感通道具有更好的线性范围和灵敏度,该方法线性范围为1~80 μmol·L^-1,检出限为0.54 μmol·L^-1。此外,MnO₂ NPs介导的荧光传感DPA应用于人体尿液样品分析中的回收率为98.31%~107.76%,证明了该方法的可靠性。     

吩噻嗪-Corrole 镓(III)配合物的合成、荧光及其光断裂DNA性质

合成了吩噻嗪(PTZ)-corrole二元体1-3及其镓(III)配合物4-6.采用稳态吸收与稳态发射及时间分辨的瞬态光谱技术研究了这几种化合物的光物理特性.结合荧光量子产率和荧光寿命计算得到它们的辐射和无辐射速率常数.稳态吸收光谱表明:几种二元体中,corrole镓(III)单元表现出更强的Soret带和Q带.化合物1-3的荧光量子产率分别是0.156、0.134和0.139,辐射速率常数分别为4.02′107、3.47′107和2.89′107s-1.化合物4-6的荧光量子产率分别是0.502、0.443和0.494,辐射速率常数分别为20.90′107、16.78′107和21.11′107s-1.可见,化合物4-6的荧光量子产率和辐射速率常数均高于化合物1-3.然而,化合物4-6的荧光寿命分别是2.40、2.64和2.34ns,低于自由corrole1-3.琼脂糖凝胶电泳实验表明:在光照的条件下,这些吩噻嗪-corrole镓(III)二元体化合物能够把超螺旋DNA(formI)切割成缺刻型DNA(formII).     

卤代苯溶剂对镓咔咯配合物光物理性质的影响:外重原子效应

利用紫外-可见光谱、稳态和时间分辨荧光光谱以及飞秒瞬态吸收光谱探测了不同卤代苯溶剂对三种五氟苯基取代的镓咔咯(1-Ga、2-Ga、3-Ga)光物理性质的影响,结果表明卤代苯溶剂的色散力对于镓咔咯电子光谱吸收峰位置的影响起着主要作用;溶剂外重原子效应能显著降低镓咔咯的荧光量子产率。飞秒瞬态吸收光谱表明,光激发下,镓咔咯与卤代苯溶剂之间可发生电子转移反应,溶剂的重原子效应可以减缓电荷分离态复合物电荷重组速率。     

Solvent, anion, and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles

A series of manganese(III) corroles were investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous solvents. Up to three oxidations and one reduction were obtained for each complex depending on the solvents. The main compound discussed in this paper is the meso-substituted manganese corrole, (Mes 2PhCor)Mn, and the main points are how changes in axially coordinated anion and solvent will affect the redox potentials and UV-vis spectra of each electrogenerated species in oxidation states of Mn(III), Mn(IV), or Mn(II). The anions OAc (-), Cl (-), CN (-), and SCN (-) were found to form five-coordinate complexes with the neutral Mn(III) corrole while two OH (-) or F (-) anions were shown to bind axially in a stepwise addition to give the five- and six-coordinate complexes in nonaqueous media. In each case, complexation with one or two anionic axial ligands led to an easier oxidation and a harder reduction as compared to the uncomplexed four-coordinate species.     

Synthesis and full characterization of molybdenum and antimony corroles and utilization of the latter complexes as very efficient catalysts for highly selective aerobic oxygenation reactions

Two molybdenum and three antimony corroles were isolated and characterized by NMR, EPR, and electrochemistry. The very negative reduction potentials of the (oxo)molybdenum(V) corroles are clearly related to their inactivity as oxygen transfer reagents and the unsuccessful attempts to isolate lower-valent molybdenum corroles. X-ray crystallography of the (oxo)molybdenum(V) corrole 1a and the trans-difluoroantimony(V) corrole 2c, the first of their kind, revealed that their molecular structures represent extreme cases of such complexes: a highly domed corrole with very large out-of-plane metal displacement for 1a (0.73 Angstroms) and a very flat corrole with the metal ion in its center for 2c. All three antimony corroles displayed high activity and selectivity as catalysts for the photoinduced oxidation of thioanisole by molecular oxygen, with superior results obtained in alcoholic solvents with 2c as catalyst. Allylic and tertiary benzylic CH bonds were also oxidized under those conditions, with absolute selectivity to the corresponding hydroperoxides.     

Photophysical properties of a series of free-base corroles

Four free-base corroles with electron-donating or electron-withdrawing groups on the para or 2 through 6-positons of the meso phenyl rings were prepared via either Paolesse or Gross conditions and investigated for their absorption and emission properties. The triaryl corroles 5,10,15-triphenylcorrole, 5,10,15-tris(pentafluorophenyl)corrole, 5,10,15-tris(p-nitrophenyl)corrole, and 5,10,15-tris(p-methoxyphenyl)corrole were examined. Absorption, steady-state, and time-resolved fluorescence measurements were performed on all compounds in both nonpolar (dichloromethane) and polar (dimethylacetamide) solvents. The experimental evidence points to hydrogen bonding with an internal N-H group as the most likely factor in the solvent-dependent photophysical behavior of these corroles, that is also highly dependent upon substitution.     

新型氯代苯基咔咯的合成及电化学和光谱性质

通过吡咯和具有相应取代基的苯甲醛在甲醇和水的混合溶剂中生成胆色烷, 然后用四氯苯醌氧化胆色烷, 合成了2种新型的咔咯化合物: 三(4-氯苯基)咔咯[(ClPh)₃CorH₃]和三(2,4-二氯苯基)咔咯[(Cl₂Ph)₃CorH₃]. 采用紫外-可见、荧光、¹H NMR、MS和IR等光谱技术对化合物进行了表征. 研究了化合物在二氯甲烷和二甲基甲酰胺中的电化学及光谱电化学性质. 讨论了溶剂和取代基对紫外-可见光谱以及氧化还原电位和电子转移过程的影响. 提出了化合物在2种不同溶剂中的氧化还原反应机理.     

Synthesis and characterization of germanium, tin, phosphorus, iron, and rhodium complexes of tris(pentafluorophenyl)corrole, and the utilization of the iron and rhodium corroles as cyclopropanation catalysts

The germanium(IV), tin(IV). and phosphorus(v) complexes of tris(pentafluorophenyl)corrole were prepared and investigated by electrochemistry for elucidation of the electrochemical HOMO-LUMO gap of the corrole and the spectroscopic characteristics of the corrole pi radical cation. This information was found to be highly valuable for assigning the oxidation states in the various iron corroles that were prepared. Two iron corroles and the rhodium(I) complex of an N-substituted corrole were fully characterized by X-ray crystallography and all the transition metal corroles were examined as cyclopropanation catalysts. All iron (except the NO-ligated) and rhodium corroles are excellent catalysts for cyclopropanation of styrene, with the latter displaying superior selectivities. An investigation of the effect of the oxidation state of the metal and its ligands leads to the conclusion that for iron corroles the catalytically active form is iron(III), while all accesible oxidation states of rhodium are active.     

两种甲氧基苯基咔咯铜配合物的合成及光谱性质

合成了两个中位苯基上具有甲氧基取代基的铜咔咯配合物(Tp-OCH3PC)Cu和(To,p-(OCH3)2PC)Cu,通过紫外-可见、红外光谱、元素分析、核磁共振及质谱对它们进行了表征。研究了配合物在非水溶剂中的电子顺磁共振、电化学和光谱电化学性质,结果表明无论在固体状态还是在非水溶剂中,配合物的中心金属离子均为三价铜Cu(Ⅲ),在给定的溶剂中Cu(Ⅲ)可以发生可逆的还原反应生成Cu(Ⅱ),也可以被可逆氧化为Cu(Ⅲ)的阳离子自由基。探讨了甲氧基取代基以及溶剂对配合物的紫外-可见光谱和氧化还原电位的影响。     

三羟基咔咯及其镓配合物与DNA的相互作用、光断裂和光动力抗肿瘤活性

合成了一个三羟基咔咯10-(4-羟基苯基)-5,15-双(4-(2-羟乙基)氨基-2,3,5,6-四氟苯基)咔咯(1)及其镓配合物(1-Ga)。光谱滴定实验、粘度测试和分子对接模拟结果表明,1和1-Ga通过外部结合模式与小牛胸腺DNA发生相互作用。琼脂糖凝胶电泳实验结果表明1和1-Ga显示出良好的光核酸酶活性。2种化合物对A549,HepG2,MCF-7肿瘤细胞有显著的光毒性。光辐照后,它们能通过活性氧物种(ROS)介导的线粒体途径诱导HepG2细胞凋亡。此外,1-Ga能使肿瘤细胞周期阻滞在G2/M期。     

Beta-octafluorocorroles

The one-pot corrole synthesis first reported by the Gross and Paolesse groups appears to have evolved into a remarkably general and predictable self-assembly based synthetic reaction. Gross's solvent-free procedure (refs 8 and 9) has proven particularly effective in our hands and, in fact, more general than originally claimed. In earlier work (ref 17), we showed that the reaction works for a variety of aromatic aldehyde starting materials and was not limited to relatively electron-deficient aldehydes, as reported by Gross and co-workers. Here, we show that the pyrrole component is also variable in that 3,4-difluoropyrrole undergoes oxidative condensation with four different p-X-substituted benzaldehydes to yield the corresponding beta-octafluoro-meso-tris(para-X-phenyl)corroles (X = CF3, H, CH3, and OCH3). Further, we have prepared the Cu and FeCl derivatives of the beta-octafluorocorrole ligands. The XPS nitrogen 1s ionization potentials of these fluorinated ligands are some 0.7 eV higher than those of the corresponding beta-unfluorinated ligands. The oxidation half-wave potentials of the Cu and FeCl complexes of the fluorinated corroles are also positively shifted by 300-400 mV relative to their beta-unsubstituted analogues, demonstrating the strongly electron-deficient character of the fluorinated ligands. 1H NMR spectroscopy suggests that like their beta-unfluorinated counterparts, the new beta-octafluorinated triarylcorroles act as substantially noninnocent ligands, i.e., exhibit corrole pi-cation radical character, in the FeCl complexes. Quantitatively, however, NMR spectroscopy and DFT calculations indicate that the beta-octafluorinated corroles are somewhat less noninnocent (i.e., carry less radical character) than their beta-unfluorinated counterparts in the FeCl complexes. Temperature-dependent 19F NMR spectroscopy suggests that the Cu octafluorocorroles have a thermally accessible paramagnetic excited state, which we assign as a Cu(II) corrole pi-cation radical. We have previously reported that the electronic absorption spectra, particularly the Soret absorption maxima, of high-valent transition metal triarylcorroles are very sensitive to the nature of the substituents in the meso positions. In contrast, the Soret absorption maxima of free-base triarylcorroles are not particularly sensitive to the nature of the meso substituents. This scenario also holds for the fluorinated corroles described here. Thus, although the four free-base fluorinated triarylcorroles exhibit practically identical Soret absorption maxima, the Soret bands of the Cu derivatives of the same corroles red-shift by approximately 35 nm on going from the p-CF3 to the p-OCH3 derivative.