萘基卟啉的合成与性能研究

以萘基醛类化合物为原料与吡咯在丙酸中回流合成了3种含萘基的新型卟啉化合物,其中2种化合物尚未见文献报道,其结构通过1H NMR,IR和UV-V is确定。与四苯基卟啉相比,萘基的引入增大了卟啉环的共轭性,使得光学吸收波长与荧光发射波长均发生不同程度的红移,Q带吸收峰形改变且激发波长增长。结合卟啉光谱四轨道理论对该变化进行了讨论。     

几种含杂环席夫碱的制备和光致变色性能的研究

用2-羟基-1-萘甲醛和含杂环胺合成出7种席夫碱,利用IR和1HNMR对其结构进行了表征。利用UV-Vis和IR研究了光致变色的性能,并且探讨了变色性能与化合物结构的关系。结果表明:虽然这7种席夫碱的亚胺基团的邻位都具有羟基,但只有2-羟基萘甲醛缩2-胺基-3-甲基吡啶和2-羟基萘甲醛缩5-甲基噻唑表现出光致变色的性能。在经历了波长为365 nm的紫外光辐射之后,2-羟基萘甲醛缩2-胺基-3-甲基吡啶的紫外光谱中λ400 nm的吸收谱带中的吸收峰的强度都不同程度降低了;2-羟基萘甲醛缩5-甲基噻唑在498 nm处出现新的吸收峰,并且随着紫外光照射时间的延长,该新吸收峰和2-羟基萘甲醛缩2-胺基-3-甲基吡啶在592 nm处的吸收峰都逐渐增强,说明光致变色的性能是由于烯醇亚胺-酮胺构型互变异构导致的。红外光谱检测结果显示,2-羟基萘甲醛缩2-胺基-3-甲基吡啶、2-羟基萘甲醛缩5-甲基噻唑在经历了紫外光辐射后,羟基氢的伸缩振动的吸收峰急剧减弱以至消失不见,而两者在1 686、1 730 cm-1处分别出现新的小的羰基伸缩振动吸收峰,此外红外光谱中指纹区的吸收也发生了比较明显的变化,这些都进一步说明烯醇亚胺-酮胺的互变异构。比较这7种席夫碱的结构可知,化合物的吡啶环上亚胺基团的邻位或者噻唑环上连接有供电子基团时,表现出光致变色性能的可能性较大。     

Br-,I-精确取代萘环1,4活化位合成及结构表征

以1-氨基萘为起始原料,乙酸酐提供保护基,在酸性条件下对氨基进行保护,形成邻对位定位基,可有效在萘环4位上精确引入溴原子,再在碱性条件下去除氨基保护基,通过重氮化法精确取代萘环上的1位来合成1-溴-4-碘萘及1,4-二溴萘。通过红外光谱、热重及紫外吸收光谱,对其结构、热稳定性及光谱吸收进行了分析。1-溴-4-碘萘的热分解温度为179℃,紫外吸收波长在230nm,285nm,296nm,306nm;1,4-二溴萘的热分解温度为187℃,紫外吸收波长在230nm,289nm,301nm,314nm。     

微波辐射磷酸催化合成2-羟基-1-萘甲醛

2-羟基-1-萘甲醛简称HNA,其作为一种重要的有机化学合成中间体,在金属络合染料,织物,油墨,橡胶用甲亚胺染料及荧光增白剂等方面有着广泛的应用。其传统合成方法主要有Duff法,Gattermann法和Reimer-Tiemann法等。本文在微波加热条件下,以磷酸代替浓硫酸作催化剂催化2-萘酚与六次甲基四胺反应合成了2-羟基-1-萘甲醛,设计了四因素三水平正交实验方案探讨合成2-羟基-1-萘甲醛的最佳工艺条件,获得最佳反应条件:反应物摩尔比2-萘酚:六次甲基四胺1∶1.3,反应时间5分钟,催化剂磷酸3 mL,微波功率500W,平均产率可以达到76.21%。     

一种新型β，β桥连双卟啉的合成与结构表征

以1,6-二溴己烷为桥连试剂,2-(1-羟基萘基)-5,10,15,20-四苯基金属卟啉为原料,合成了两个新型双卟啉.并用IR、1HNMR、MS、UV-Vis光谱及EA对目标化合物的结构进行了表征.     

4-烯丙氧基萘酰亚胺的合成与光学性质研究

以4-溴-1,8-萘二甲酸酐为原料,与正丁胺反应生成4-溴萘酰亚胺,再与甲醇钠在硫酸铜的作用下反应,生成4-甲氧基萘酰亚胺,经HI作用,脱去保护得到4-羟基萘酰亚胺,最后与3-溴丙烯反应合成了目标化合物。结构经~1HNMR、~(13)CNMR、MS等加以表征,并对其吸收与荧光性质进行测定。结果表明,目标化合物收率为78%,紫外吸收波长为370 nm,荧光发射峰波长为450 nm。对HepG2细胞进行染色,激发后细胞呈现出强烈的蓝色荧光,成功实现细胞内荧光成像,具有良好的生物应用前景。     

“一锅法”合成2-羟基-1-萘甲醛技术研究

以2-萘酚和氯仿为原料,甲醇为溶剂,在新的相转移催化剂和碱性条件下应用"一锅法"合成技术合成了2-羟基-1-萘甲醛。研究了原料配比、反应时间、反应温度、相转移催化剂用量等因素对反应的影响,获得的最佳合成条件是:2-萘酚0.028 mol,氯仿0.084 mol,相转移催化剂用量为0.25g,40%NaOH溶液为12 mL,反应温度76℃,反应时间60 min,2-羟基-1-萘甲醛的收率达到58.7%。     

N-(甲基取代苯基)-N′-(2-羟基-3-萘甲酰基)脲的合成研究

以2-羟基-3-萘甲酸和二氯亚砜为原料合成2-羟基-3-萘甲酰氯,再与甲基取代的苯脲化合物反应得到N-(甲基取代苯基)-N′-(2-羟基-3-萘甲酰基)脲。重点研究了N-(3-甲基苯基)-N-(′2-羟基-3-萘甲酰基)脲的合成工艺条件对产品收率的影响,确定了最佳合成工艺,即以苯为溶剂、三乙胺为缚酸剂,n(间甲基苯脲)∶n(2-羟基-3-萘甲酰氯)∶n(苯)=1∶3∶33,回流温度下反应4 h,产品质量分数97.40%,收率71.5%。在相同条件下合成了N-(2-甲基苯基)-N′-(2-羟基-3-萘甲酰基)脲、N-(4-甲基苯基)-N-(′2-羟基-3-萘甲酰基)脲和N-(3,5-二甲基苯基)-N-′(2-羟基-3-萘甲酰基)脲,质量分数分别为95.72%、97.69%和99.44%,收率分别为47.1%、71.5%和59.7%。通过紫外吸收光谱、红外吸收光谱和质谱等对化合物进行了表征,证明产品结构正确。     

(S)-2'-甲氧基-2-丙烯酰基-1,1'-联萘的合成

以1-羟基-2-萘甲酸与2-甲氧基萘为起始原料通过多步反应合成了标题化合物。首先将1-羟基-2-萘甲酸转化为1-(-)-薄荷氧基-2-萘甲酸-(-)-薄荷酯,再将2-甲氧基萘转化为1-溴-2-甲氧基萘,1-溴-2-甲氧基萘的格氏试剂与酯反应得到(S)-2'-甲氧基-1,1'-联萘-2-甲酸-(-)-薄荷酯。该薄荷酯再经还原反应、氧化反应、加成反应、氧化反应得到标题化合物。对各步反应的实验条件进行了适当改进,找到了较好的合成条件,并用1HNMR和13CNMR对各步产物进行了表征。     

偶氮卟啉染料的制备及性能研究

以meso-四(4-硝基苯基)卟啉为原料经硝基还原后制得meso-四(4-氨基苯基)卟啉,meso-四(4-氨基苯基)卟啉再经重氮化后分别与2-萘酚和8-羟基喹啉发生偶合反应得到meso-四[4-(2-羟基偶氮萘基)苯基]卟啉(卟啉1)和meso-四[4-(8-羟基偶氮喹啉)苯基]卟啉(卟啉2)。利用核磁共振氢谱、IR、UV-Vis、循环伏安法等确定了目标化合物的结构、光谱特征和电化学性能。紫外-可见光光谱测试结果表明,卟啉1和卟啉2的Q带与meso-四(4-氨基苯基)卟啉相比,吸收强度明显增强,并且卟啉2与卟啉1相比,在可见光区有明显的红移现象。用循环伏安法研究了两种偶氮卟啉染料的氧化还原性质,通过计算ELUMO和EHOMO值,得出其能级结构与纳米TiO_2的导带能级相匹配。     

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。     

Identification of fatty acid polymorphic modifications by infrared spectroscopy

IR spectra in the 7.5–25.0 μ region are shown to be unique for the individual long chain odd carbon numbered saturated fatty acids and for the monounsaturated even carbon numbered fatty acids, their isomers, and polymorphic modifications. IR spectra are presented which illustrate similarites and dissimilarities resulting from chain length differences and polymorphic variations for monounsaturated acids. X-ray crystal long spacings for the saturated odd carbon numbered acids are compared with literature values. X-ray crystal long spacings for monounsaturatedtrans acids are shown to be related to carbon chain length and independent of the location of unsaturation. Diffractograms and IR spectra of the 2 polymorphic modifications of elaidic acids are presented. IR spectra illustrating band differences forcis andtrans isomers are shown. ARS, USDA.     

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.     

酰胺基卟啉化合物的制备、表征及热分析

5-(4-氨基)苯基-10,15,20-三苯基卟啉(MATPP)与棕榈酸在CH2Cl2中直接反应,得到一种新型不对称酰胺基卟啉5-(4-棕榈酸酰亚胺基)苯基-10,15,20-三苯基卟啉(PITPPH2),利用紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等测试方法对化合物的结构加以确认。热分析表明,卟啉PITPPH2从200℃开始分解,具有较高的热稳定性。     

Porphyrin migration and aggregation in a poly(methylmethacrylate) matrix

The aging of thin polymer films is interesting for the development of nonlinear optical media. In this study, the optical properties of porphyrin‐doped poly(methylmethacrylate) (PMMA) films are investigated before and after annealing. Both absorption and luminescence spectroscopies were used to characterize the changes that occurred during the thermal treatment. The surface and bulk characteristics of the doped films were also measured using atomic force microscopy, X‐ray‐induced photoelectron spectra, and DSC. We found that the aging of the thin polymer films led the porphyrin molecules to diffuse in the direction of the polymer surface. This led to the random formation of porphyrin aggregates on the surface, followed by absorption band shift and little luminescence quenching. These results suggest that porphyrin‐doped PMMA films could be used as long‐term stable active optical materials. POLYM. COMPOS., 35:665–670, 2014. © 2013 Society of Plastics Engineers     

The synthesis and properties of meso-tetra(4-alkylamidophenyl)porphyrin liquid crystals and their Zn complexes

A series of novel, long-chain-substituted, porphyrin derivatives, meso-tetra (4-alkylamidophenyl) porphyrin ligands and their Zn complexes (alkyl = 8, 10, 12, 14, 16,18) were prepared by acylation of the amino groups of 5,10,15,20-tetra(4-aminophenyl)porphyrin by alkyl chloride. Mesomorphism was investigated by DSC, polarized optical microscopy (POM) and X-ray diffraction (XRD). Only ligands containing chains >12 carbon atoms displayed liquid crystalline behaviour, which exhibited a high phase transition temperature and a broad mesophase temperature span, Zn complexes showed no liquid crystalline behaviour. Cyclic voltammetry, luminescence spectra and surface photovoltage spectroscopy revealed that covalent linking of an alkylamido group to the tetraphenylporphyrin molecule influences, significantly, the properties of the porphyrin macrocycle.     

Doping behavior of single-walled carbon nanotubes with differently charged porphyrins

Photoluminescence (PL) measurements of porphyrin-doped single-walled carbon nanotubes (SWCNTs) were performed in sodium dodecylbenzenesulfonate (NaDDBS) aqueous dispersions. PL spectra were used to draw PL maps in which maxima correspond to absorption-emission excitonic processes related to (E11, E22) first Van Hove singularities of the SWCNT electronic structure. The influence of the net charge of the porphyrin is a determining factor in the energy map maximum shifts (EMMS) relative to that of a pristine NaDDBS/SWCNT dispersion. A non-interacting porphyrin is used as a reference to discard the influence of the dielectric constant of the medium in the EMMS.     

A Novel Soluble Tin(IV) Porphyrin Modified Single-Walled Carbon Nanotube Nanohybrid With Light Harvesting Properties

A dihydroxotin(IV) porphyrin functionalized single-walled carbon nanotubes (SWNTs) nanohybrid is obtained. Solubility of the nanohybrid in organic solvents is determined by UV-Vis-NIR absorption spectroscopy. Electron absorption and fluorescence spectra investigations demonstrate that efficient electron transfer occurs within the nanohybrid at the photoexcited state and the charge-separated state of the nanohybrid is observed by transient absorption spectrum. The results illustrate that this soluble electron donor–acceptor nanohybrid might be a good candidate as a light harvesting material in molecular photoelectronic devices.     

聚合物键联钴卟啉的合成及其催化作用

合成了 5 -对羟苯基 - 1 0 ,1 5 ,2 0 -三 (对甲氧苯基 )卟啉 (1 )及其钴配合物 (2 )。将(1 )与氯甲基化聚苯乙烯树脂键合得聚合物键联卟啉 (3) ,(3)与钴离子络合得聚合物键联钴卟啉 (4) ,考察了 (4)对丙硫醇的催化氧化作用。对卟啉化合物进行了 IR、UV测定和元素分析。对丙硫醇氧化产物作了 HPL C、UV、IR和 MS分析。