带有12条柔性长链的卟啉及其金属配合物的合成及液晶性质的研究

以简单化合物为原料,经过多步反应合成出一种新型的、带有12条肉豆蔻酰氧基取代柔性长链的卟啉配体,并通过与过渡金属盐反应,得到卟啉金属锌、铜配合物。所合成的化合物经红外光谱、紫外-可见吸收光谱、~1HNMR等进行表征。通过荧光发射光谱、荧光寿命等进行了光学性质研究,并通过差示扫描量热法和偏光显微镜研究了化合物的液晶性质。结果表明,卟啉配体与铜配合物是双变液晶,而锌配合物在升温时呈现液晶相。化合物液晶相的相变温度较低,相变区间较窄。     

一种长链卟啉的合成、表征及液晶性质研究

文章通过一系列反应,合成出一种带有八条柔性长链的卟啉化合物,并合成出该卟啉的锌、铜金属配合物。通过紫外-可见光谱、红外光谱、核磁共振氢谱等对化合物进行表征,并研究了它们的荧光性质和液晶性质。     

meso-四-(4-辛氧基-3-甲氧基苯基)卟啉及其金属配合物的合成与表征

报道了一种新型对称型卟啉化合物meso-四-(4-辛氧基-3-甲氧基苯基)卟啉(TOMPPPH2)及其金属钌、钯配合物(Ru(DMF)2TOMPPP,PdTOMPPP)的合成,并通过可见光谱,红外光谱,核磁共振氢谱和元素分析等对这些卟啉化合物的结构进行了表征。     

5-(4-吡嗪甲酰胺基)苯基-10,15,20-三苯基卟啉和锌配合物的合成及热分析

合成了新型5-(4-吡嗪甲酰胺基)苯基-10,15,20-三苯基卟啉配体(H2P)及其锌配合物(ZnP),通过元素分析、质谱、紫外-可见光谱、核磁共振氢谱、红外光谱对其组成和结构进行分析表征。热分析表明,卟啉配体从410℃开始分解,具有较高的热稳定性。     

吡啶氧丁氧苯基三甲氧苯基卟啉及其Fe(Ⅲ)配合物的合成与表征

报道了一种新型尾式卟啉化合物 - 5 -对 [4- (间吡啶氧基 )丁氧基 ]苯基 - 1 0 ,1 5 ,2 0 -三对甲氧苯基卟啉及其 Fe( )配合物的合成。并通过元素分析、红外光谱、核磁共振光谱及紫外可见光谱等对其结构进行了表征     

新型L-亮氨酸尾式卟啉及其锌(Ⅱ)配合物的合成与表征

合成了一种新型L-亮氨酸尾式卟啉及其锌(Ⅱ)配合物,通过元素分析、红外光谱、紫外-可见光谱和质谱等对其进行了结构表征。测试并研究了它们在4000～400cm^-1范围内的傅里叶变换红外光谱。     

尾式甲氧苯基卟啉及其Fe(Ⅲ)配合物的合成与表征

本文所报道的是一种新型尾式卟啉化合物——5-对[4-（间吡啶氧基）丁氧基]苯基-10,15,20-三对甲氧苯工卟啉及其Fe(Ⅲ）配合物的合成。并通过元素分析、红外光谱、核磁共振谱及紫外可见光谱等对其结构进行了表征。     

镍卟啉配合物[Ni(bpy)(t-BuOPTPP)]的合成与表征

报道了一种新型尾式卟啉化合物5-(4-叔丁氧基苯基)-10、15、20-三苯基卟啉[H2(t-BuPTPP)]及其Ni(bpy)^2 配合物的合成,并通过元素分析、红外光谱、核磁共振氢谱及紫外可见光谱等对其结构进行了表征。     

新型L-苏氨酸尾式卟啉及其锌(II)配合物合成与表征

为了探索手性金属卟啉配合物的结构与功能 ,用 L-苏氨酸和 5 -[邻 -(2 -溴乙氧基 )苯基 ]-1 0 ,1 5 ,2 0 -三苯基卟啉为原料合成了一种新型 L-苏氨酸尾式卟啉及其锌 (II)配合物 ,通过元素分析、红外光谱、化学分析和质谱等对其进行了结构表征。测试并研究了它们在 40 0 0～ 40 0 cm- 1 范围内的傅里叶变换红外光谱 ,对主要谱带进行了经验归属     

两种尾式卟啉及其金属钯配合物的合成与表征

合成了尾式卟啉化合物5-(2-戊烷氧基苯基)-10,15,20-三(对氯苯基)卟啉和5-(2-异戊氧基苯基)-10,15,20-三(对氯苯基)卟啉及其金属钯配合物并通过元素分析、紫外-可见光谱、红外光谱和核磁共振氢谱对这些卟啉化合物的结构进行了表征。     

手性硅宁—卟啉配体的合成与表征

首次合成了３种新的手性硅宁－卟啉配体。它们的结构分别用紫外可见光谱、核磁共振谱、红外光谱和质谱进行了表征。     

不对称席夫碱Cu(Ⅱ)配合物的合成和催化性能研究

用2,4-二羟基苯乙酮、二胺基硫脲与取代水杨醛反应,合成了3种不对称席夫碱配体及其Cu(Ⅱ)配合物,通过元素分析、1HNMR、IR、UV-vis、MS等手段对配体及其配合物进行了组成和结构表征,并研究了不对称席夫化合物对双氧水的催化分解性能。结果表明,合成得到的不对称席夫碱Cu(Ⅱ)配合物对催化H2O2分解具有较好的催化性能。     

β-萘并冠醚卟啉的合成及光敏活性

以2,3-二羟基萘基四苯基卟啉及其Cu（Ⅱ）配合物为原料制备了一类新型9-冠-3-四苯基卟啉,通过紫外可见吸收光谱、红外光谱、质谱、核磁共振氢谱等测试手段对冠醚卟啉进行结构表征,研究了冠醚卟啉产生单线态氧的能力、与DNA的相互作用及其对pBR322质粒DNA的切割。结果表明,冠醚卟啉具有明显的产生单线态氧的能力;与DNA的相互作用模式为外部自堆积;对DNA有较明显的切割效果。     

The Structural Chemistry of Metallocorroles: Combined X-ray Crystallography and Quantum Chemistry Studies Afford Unique Insights

Although they share some superficial structural similarities with porphyrins, corroles, trianionic ligands with contracted cores, give rise to fundamentally different transition metal complexes in comparison with the dianionic porphyrins. Many metallocorroles are formally high-valent, although a good fraction of them are also noninnocent, with significant corrole radical character. These electronic-structural characteristics result in a variety of fascinating spectroscopic behavior, including highly characteristic, paramagnetically shifted NMR spectra and textbook cases of charge-transfer spectra. Although our early research on corroles focused on spectroscopy, we soon learned that the geometric structures of metallocorroles provide a fascinating window into their electronic-structural characteristics. Thus, we used X-ray structure determinations and quantum chemical studies, chiefly using DFT, to obtain a comprehensive understanding of metallocorrole geometric and electronic structures. This Account describes our studies of the structural chemistry of metallocorroles. At first blush, the planar or mildly domed structure of metallocorroles might appear somewhat uninteresting particularly when compared to metalloporphyrins. Metalloporphyrins, especially sterically hindered ones, are routinely ruffled or saddled, but the missing meso carbon apparently makes the corrole skeleton much more resistant to nonplanar distortions. Ruffling, where the pyrrole rings are alternately twisted about the M-N bonds, is energetically impossible for metallocorroles. Saddling is also uncommon; thus, a number of sterically hindered, fully substituted metallocorroles exhibit almost perfectly planar macrocycle cores. Against this backdrop, copper corroles stand out as an important exception. As a result of an energetically favorable Cu(d(x2-y2))-corrole(π) orbital interaction, copper corroles, even sterically unhindered ones, are inherently saddled. Sterically hindered substituents accentuate this effect, sometimes dramatically. Thus, a crystal structure of a copper β-octakis(trifluoromethyl)-meso-triarylcorrole complex exhibits nearly orthogonal, adjacent pyrrole rings. Intriguingly, the formally isoelectronic silver and gold corroles are much less saddled than their copper congeners because the high orbital energy of the valence d(x2-y2) orbital discourages overlap with the corrole π orbital. A crystal structure of a gold β-octakis(trifluoromethyl)-meso-triarylcorrole complex exhibits a perfectly planar corrole core, which translates to a difference of 85° in the saddling dihedral angles between analogous copper and gold complexes. Gratifyingly, electrochemical, spectroscopic, and quantum chemical studies provide a coherent, theoretical underpinning for these fascinating structural phenomena. With the development of facile one-pot syntheses of corrole macrocycles in the last 10-15 years, corroles are now almost as readily accessible as porphyrins. Like porphyrins, corroles are promising building blocks for supramolecular constructs such as liquid crystals and metal-organic frameworks. However, because of their symmetry properties, corrole-based supramolecular constructs will probably differ substantially from porphyrin-based ones. We are particularly interested in exploiting the inherently saddled, chiral architectures of copper corroles to create novel oriented materials such as chiral liquid crystals. We trust that the fundamental structural principles uncovered in this Account will prove useful as we explore these fascinating avenues.     

新型PMNAP缩胺类席夫碱及其铜配合物的合成与表征

在非水溶剂中合成了3种基于1-苯基-3-甲基-4-萘乙酰基-5-吡唑啉酮(PMNAP)缩胺类新型席夫碱及其铜配合物。由元素分析、络合滴定法、质谱和摩尔电导值推测出配合物的组成为CuL2[L=L1,L2,L3],通过红外光谱、紫外光谱、热重分析和核磁共振氢谱对配体和配合物进行了结构表征。结果表明:在测试条件下,3种新配体均以酮式和烯醇式结构共存,配位时酮式可能转化为烯醇式结构按去质子的方式以烯醇负离子的O和亚胺基上的N与铜中心离子配位,配合物的配位数均为4。     

胡椒醛缩合卟啉化合物的合成及其光谱性能

以胡椒醛及羟基芳香醛为原料与吡咯在丙酸中回流,合成了6种卟啉化合物,其结构用1HNMR,IR,UV-V is和ESI-MS确定。与四苯基卟啉(TPP)相比,胡椒醛的引入增大了卟啉环的共轭性,使几种化合物的光学吸收波长均发生不同程度的红移,其中,Soret带最大红移11 nm;同时,胡椒醛的引入缩小了基态与激发态之间的能极差,化合物荧光发射波长发生1~5 nm的红移。     

Self-assembly of novel tris(p-carboxyphenyl) porphyrin monomer and its copolymers with acrylamide in aqueous media

The novel porphyrin monomer 5-(4-acryloyloxylphenyl)-10,15,20-tris(4-carboxyphenyl)porphyrinate zinc(II) (ZnAOTCPP) and its corresponding sodium salt (ZnAOTCPP-Na) were synthesized. The latter compound exhibited a new band in excitation spectra due to formation of porphyrin aggregates in water, which were derived from its surface-activity when the concentration was higher than its critical association concentration (CAC). The porphyrins were copolymerized with acrylamide (AM) to prepare water-soluble copolymers with random and micro-blocky structures, which all displayed very new absorption and fluorescence emission bands in the long wavelength region compared with the porphyrin monomer. Furthermore, the micro-blocky copolymer exhibited an additional new absorption band at even longer wavelength region compared with the random copolymer. The experimental results and analysis showed that the porphyrin units in the random copolymer chains self-assembled to form porphyrin association complexes by hydrophobic association and π-π stacking interactions, and covalent restrictions of polymer chains in the micro-blocky copolymer.     

The synthesis and catalytic activity to Li/SOCl2 battery of two new porphyrins

Two new porphyrins (3a, 3b) were synthesized and characterized by IR, UV–vis, ¹H NMR, MS and elementary analysis. The catalytic activity of the synthesized porphyrins to lithium/thionyl chloride (Li/SOCl₂) battery is evaluated by the relative energy of the battery whose electrolyte contains the porphyrins. The results indicate that the energy of Li/SOCl₂ battery catalyzed by porphyrins 3a and 3b is 101, 37% higher, respectively, than that of Li/SOCl₂ battery in the absence of the porphyrins. It can be used as a basis for the synthesis of more porphyrins with improved catalytic activity to Li/SOCl₂ battery in the future.     

四-(邻/对-氯苯基)金属卟啉的合成

以邻／对氯苯甲醛为主要原料合成了６个四氯取代四苯基金属卟啉类化合物，其中４个是尚未见文献报道的新化 物，并用红外、紫外可见光谱、质谱等分析手段对其主要基团及结构进行了表征，证明其结构正确。     

Synthesis and spectral evaluation of some unsymmetrical mesoporphyrinic complexes

Synthesis and spectral evaluation of new zinc and copper unsymmetrical mesoporphyrinic complexes are reported. Zn(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Zn(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin, Cu(II)-5-(4-acetoxy-3-methoxyphenyl)-10,15,20- tris-(4-carboxymethylphenyl)porphyrin and Cu(II)-5-[(3,4-methylenedioxy)phenyl]-10,15,20- tris-(4-carboxymethylphenyl)porphyrin were synthesized using microwave-assisted synthesis. The complexes were characterized by elemental analysis, FT-IR, UV-Vis, EPR and NMR spectroscopy, which fully confirmed their structure. The spectral absorption properties of the porphyrinic complexes were studied in solvents with different polarities. Fluorescence emission and singlet oxygen formation quantum yields were evaluated for the compounds under study, revealing high yields for the zinc derivatives. The copper complexes are not emissive and only display residual capacity for singlet oxygen formation.