芳氧基取代酞菁锌的合成及光物理化学性质

合成得到3-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、4-(5-氨基-萘氧基)邻苯二甲腈(C18H11N3O)、3-联苯氧基邻苯二甲腈(C20H12N2O)及4-联苯氧基邻苯二甲腈(C20H12N2O)4种未见报导的取代邻苯二甲腈,以此为前躯体合成了四[α-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[β-(5-氨基-萘氧基)]酞菁锌(C72H44N12O4Zn)、四[α-(联苯氧基)]酞菁锌(C80H48N8O4Zn)和四[β-(联苯氧基)]酞菁锌(C80H48N8O4Zn)4种未见报导的芳氧基取代酞菁锌配合物。通过测定它们的紫外-可见吸收光谱、荧光发射光谱,获得其最大吸收波长及其摩尔消光系数、最大发射波长、荧光量子产率(ΦF)、单线态氧量子产率(ΦΔ)及光降解速率常数并与其类似物进行了比较,探讨了它们的光物理光化学性质的构效关系。研究结果表明四[α-(联苯氧基)]酞菁锌在红光区具有大的摩尔消光系数,且具有较高的ΦΔ,有望开发成为光动力治疗用光敏剂。     

新型不对称镍酞菁的合成、表征及光电性质

通过改进传统的酞菁合成方法, 得到了一种新的不对称酞菁2-(4-异丙基苯氧基)-9(10),16(17), 23(24)-三(4-叔丁基苯氧基)酞菁镍(简称NiPc2), 并通过质谱、红外光谱及紫外-可见-近红外光谱对其进行了表征, 分析了其可能的形成机理以及循环伏安性质. 这种新的不对称酞菁在近红外光区有明显的吸收峰, 并且其固体紫外-可见光谱的Q带发生红移, 说明形成了J-聚集体.     

二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡(IV)酞菁的合成与表征

以3-硝基邻苯二甲腈为起始原料,与正戊醇反应合成3-戊氧基邻苯二甲腈(1),然后在高温溶剂1-氯萘中经缩聚反应合成二氯-轴向取代-四-α-(3-戊氧基)锡酞菁(2),2进一步与2-羟基吡啶在N,N-二甲基甲酰胺中合成二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡酞菁配合物3,同时对相关化合物分别进行了元素分析,IR,1HNMR,UV/Vis,荧光和质谱表征.     

具有Frétchet树枝结构的新型酞菁锌(Ⅱ)配合物:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(Ⅱ)的合成与表征

报道了一种新型Frétchet树枝配体取代酞菁锌(II)配合物:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(II)的合成与表征.首先将对氰基苄溴与3,5-二羟基苯甲醇通过Frétchet反应合成3,5-[二-(4-氰基苯甲氧基)]苯甲醇(1),1与四溴化碳和三苯基膦在四氢呋喃中反应合成3,5-二-(4-氰基苯甲氧基)苄溴(2),2与3,5-二羟基苯甲醇反应合成3,5-二-[3,5-二-(4-氰基苯甲氧基)苯甲氧基]苯甲醇(3),接着,3与4-硝基邻苯二甲腈合成"前驱物"四-{3,5-[二-(4-氰基苯甲氧基)]}苯甲氧基邻苯二甲腈(4),然后以1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)为催化剂,醋酸锌为模板剂,4通过缩聚反应合成氰基端基的Frétchet树枝配体取代酞菁锌四-{3,5-二-[3,5-二-(4-氰基苯甲氧基)苯甲氧基]-苯甲氧基}锌酞菁配合物5,最后,5的氰基端基在NaOH溶液中水解为相应的以羧基端基Frétchet树枝配体取代酞菁锌:四-{3,5-二-[3,5-二-(4-羧基苯甲氧基)苯甲氧基]-苯甲氧基}酞菁锌(II)(6).采用元素分析,IR,1H NMR,ESI-MS和MALDI-TOF-MS表征所有化合物的结构,通过UV/Vis,稳态和瞬态荧光光谱法研究了5和6的光物理性质.5和6是一类性能较好的树枝状酞菁光敏剂.     

轴向取代邻苯二氧-四-α-(戊氧基)钛酞菁配合物的合成

以1-氯萘为溶剂,3-戊氧基邻苯二甲腈与TICl4经高温缩合反应制备四-α-(戊氧基)钛氧酞菁(2);2与邻苯二酚反应合成了新型轴向取代邻苯二氧-四-α-(戊氧基)钛酞菁配合物,其结构经荧光光谱,UV-Vis,1H NMR,IR,MS和元素分析表征.     

以二苯甲酮为端基的第一代树状取代酞菁锌的合成

4-甲基二苯甲酮经N-溴代丁二酰亚胺溴代制得4-溴甲基二苯甲酮(1);1与3,5-二羟基苯甲醇反应合成了外围带有二苯甲酮取代基的第一代树枝状分子3,5-二(二苯甲酮-4-甲氧基)苯甲醇(2);2与4-硝基邻苯二甲腈缩合制得外围带有二苯甲酮取代基的第一代树枝状分子4-[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]邻苯二甲腈(3);3经"液相法"环合生成外围带有二苯甲酮取代基的第一代树枝状分子取代的酞菁锌配合物——四[3,5-二(二苯甲酮-4-甲氧基)苯甲氧基]锌酞菁[ZnPc(C35H27O5)4],其结构经UV,1HNMR,IR和MS表征。     

二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡(IV)酞菁的合成与表征

以3-硝基邻苯二甲腈为起始原料, 与正戊醇反应合成3-戊氧基邻苯二甲腈(1), 然后在高温溶剂1-氯萘中经缩聚反应合成二氯-轴向取代-四-α-(3-戊氧基)锡酞菁(2), 2进一步与2-羟基吡啶在N,N-二甲基甲酰胺中合成二-吡啶氧基-轴向取代-四-α-(3-戊氧基)锡酞菁配合物3, 同时对相关化合物分别进行了元素分析, IR, ¹H NMR, UV/Vis, 荧光和质谱表征.     

负载芳基苄醚树枝形酞菁锌聚合物纳米粒子的合成及其离体光动力活性

首先将对氰基溴化苄与3,5-二羟基苯甲醇通过Frétchet反应合成芳基苄醚树枝分子3,5[二-(4'-氰基苯甲氧基)]苯甲醇(1),1与4-硝基邻苯二甲腈合成前驱物4-{3',5'-[二-(4"-氰基苯甲氧基)]}苯甲氧基邻苯二甲腈(3),然后3在乙酸锌,1,8-二氮杂二环(5,4,0)-7-十一烯(DBU)和正戊醇...     

萘氧桥香豆素-双核锌酞菁的合成与性能研究

以1,5-二羟基萘、4-硝基邻苯二甲腈、间苯二酚、乙酰乙酸乙酯以及醋酸锌为主要原料,合成了9(10),16(17),23(24)-三[4-甲基-7-香豆素氧基]-2(3)-(1,5-二氧基萘)双核锌酞菁(bi-CPc).利用1H NMR、FT-IR、UV-Vis、元素分析、热重分析等手段对前驱体和bi-CPc的结构和性能进行表征.结果表明,bi-CPc的紫外可见吸收光谱表现出强烈的π-π*跃迁且在N,N-二甲基甲酰胺(DMF)溶液中以单体形式存在,并且具有良好的热稳定性.用循环伏安法研究了bi-CPc的氧化还原行为,计算其LUMO和HOMO能级与纳米Ti O2能级匹配.通过进一步结构修饰,有望作为性能良好的光敏染料用于太阳能电池.     

不对称三苯胺-锌酞菁的合成及性能研究

以对氨基酚、对硝基氯苯、8-羟基喹啉、4-硝基邻苯二甲腈以及醋酸锌为主要原料,合成了不对称2(3)-[二(对硝基苯基)氨基苯氧基]-9(10),16(17),23(24)-三(8-喹啉氧)锌酞菁(TQPc).用核磁、红外、元素分析等表征TQPc以及前驱化合物结构,TQPc的电子吸收光谱表现出了强烈的π-π*跃迁现象.利用紫外光谱研究了其N,N-二甲基甲酰胺(DMF)和CH2Cl2溶液的吸收光谱性质,结果表明在DMF中主要以单体的形式存在,浓度在0.223×10-5～2.587×10-5mol/L时,TQPc在CH2Cl2溶液中有二聚体的存在,经计算得到平衡常数为0.24×105L/mol.用循环伏安法研究了TQPc的氧化还原行为,结合差分伏安数据计算了能级结构,LUMO(-1.04 V vs SCE)和HOMO(0.78 V vs SCE)与纳米TiO2导带能级匹配,可作为性能较好的电荷传输材料用于染料敏化太阳能电池.     

Preparation of Langmuir–Blodgett monolayer films of (zinc(II) phthalocyanine)-containing cellulose derivative; the use of 2,3-di-O-myristyl cellulose as a scaffold

The 6-O-phthalocyanine cellulose derivative, 2,3-di-O-myristyl-6-O-[p-(9(10),16(17),23(24)-tri-tert-butyl-2-zinc(II)phthalocyaninyl-benzoyl)cellulose (8e) was synthesized in a high yield with the degree of substitution of 0.33 for the phthalocyaninyl group (DS_{phthalocyanine}) via the esterification of 2,3-di-O-myristyl cellulose (1) with the mono-substituted phthalocyanine derivative ([9(10),16(17),23(24)-tri-tert-butyl-2-[4-(carboxy)phenoxy]phthalocyaninato]zinc(II), 7). A chloroform solution of compound 8e was more stable under illumination than that of low molecular weight phthalocyanine, [2(3),9(10),16(17),23(24)-tetrakis(tert-butyl)phthalocyaninato]zinc(II). Langmuir–Blodgett (LB) monolayer films of compound 8e were prepared on a variety of different substrates using the vertical dipping method with an annealing time of 5 min. An LB monolayer film of compound 8e on an indium tin oxide (ITO) electrode exhibited a photocurrent generation performance in the range of 600–700 nm. The photocurrent density of the film composed of 8e at 680 nm was better than that of 2,3-di-O-myristyl-6-O-(zinc(II) phthalocyaninyl) cellulose (3) which was the corresponding phthalocyanine-containing cellulose synthesized through a phthalocyanine-ring forming reaction on the cellulose backbone according to an existing procedure.     

Synthesis of trimethylammoniumphenylthio-substituted phthalocyanines with different pattern of substitution

The base-catalyzed cyclotetramerization of 3-, 4- and 4,5-dimethylaminophenylthio phthalonitriles with zinc(II)acetate afforded 1(4),8(11),15(18),22(25)- and 2(3),9(10),16(17),23(24)-tetrasubstituted and 2,3,9,10,16,17,23,24-octasubstituted Zn(II)phthalocyanines, respectively. The statistical mixed condensation of the same phthalonitriles with 1,2-dicyanobenzene gave the corresponding mono- and disubstituted derivatives. Methylation of such products afforded a series of cationic Zn(II)phthalocyanines with different pattern of substitution, with potential use as photodynamic agents in microbial infections.     

A new polymeric phthalocyanine containing 16-membered tetrathia macrocyclic moieties by microwave irradiation: Synthesis and characterization

Tetranitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer with 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile in 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I)-phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II) and Cu(I) in DMAE. Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetates of Zn(II) in DMAE. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.     

Controlling the directionality of charge transfer in phthalocyaninato zinc sensitizer for a dye-sensitized solar cell: density functional theory studies

Density functional theory (DFT) calculation on the molecular structures, charge distribution, molecular orbitals, electronic absorption spectra of a series of eight unsymmetrical phthalocyaninato zinc complexes with one peripheral (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent at 2 or 3 position as an electron-withdrawing group and a different number of electron-donating amino groups at the remaining peripheral positions (9, 10, 16, 17, 23, 24) of the phthalocyanine ring, namely ZnPc-β-A, ZnPc-β-A-I-NH(2), ZnPc-β-A-II-NH(2), ZnPc-β-A-III-NH(2), ZnPc-β-A-I,II-NH(2), ZnPc-β-A-I,III-NH(2), ZnPc-β-A-II,III-NH(2), and ZnPc-β-A-I,II,III-NH(2), reveals the effects of amino groups on the charge transfer properties of these phthalocyanine derivatives with a typical D-π-A electronic structure. The introduction of amino groups was revealed altering of the atomic charge distribution, lifting the frontier molecular orbital level, red-shift of the near-IR bands in the electronic absorption spectra, and finally resulting in enhanced charge transfer directionality for the phthalocyanine compounds. Along with the increase of the peripheral amino groups at the phthalocyanine ring from 0, 2, 4, to 6, the dihedral angle between the phthalocyanine ring and the average plane of the (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent increases from 0 to 3.3° in an irregular manner. This is in good contrast to the regular and significant change in the charge distribution, destabilization of frontier orbital energies, and red shift of near-IR bands of phthalocyanine compounds along the same order. In addition, comparative studies indicate the smaller effect of incorporating two amino groups onto the 16 and 17 than on 9 and 10 or 23 and 24 peripheral positions of the phthalocyanine ring onto the aforementioned electronic properties, suggesting the least effect on tuning the charge transfer property of the phthalocyanine compound via introducing two electron-donating amino groups onto the 16 and 17 peripheral positions. As expected, compound ZnPc-β-A-I,III-NH(2) with four amino groups at 9, 10, 23, and 24 positions of the phthalocyanine ring shows the best charge transfer directionality among the three phthalocyaninato zinc complexes with four peripheral amino groups.     

Photocatalytic transformation of 4-nitrophenol in aqueous media using suspended,water-insoluble metallophthalocyanine complexes

Unsubstituted magnesium (MgPc), zinc (ZnPc) and chloroaluminium (ClAlPc) phthalocyanine complexes and the ring substituted zinc tetranitro (ZnPc(NO₂)₄), zinc tetraamino (ZnPc(NH₂)₄), zinc hexadecafluoro (ZnPcF₁₆) and zinc hexadecachloro (ZnPcCl₁₆), phthalocyanine complexes are employed as photocatalysts for the heterogeneous transformation of 4-nitrophenol (4-Np) to fumaric acid and 4-nitrocatechol. ClAlPc is the best catalyst, with 89 ± 8% degradation of 4-Np after 100 min. The least effective catalysts were ZnPcCl₁₆ and MgPc.     

Inhibitory effects of constituents from Euphorbia lunulata on differentiation of 3T3-L1 cells and nitric oxide production in RAW264.7 cells

A new flavonol galactopyranoside, myricetin 3-O-(2',3'-digalloyl)-β-D-galactopyranoide (1), and 23 known constituents, including myricetin 3-O-(2'-galloyl)-β-D-galactopyranoide (2), myricitrin (3), myricetin (4), quercetin 3-O-(2', 3'-digalloyl)-β-D-galactopyranoide (5), quercetin 3-O-(2'-galloyl)-β-D-galactopyranoide (6), hyperin (7), isoquercetrin (8), quercetin (9), kaempferol (10), apigenin (11), luteolin (12), 3-O-methylquercetin (13), 5,7,2',5'-tetrahydroxyflavone (14), 1,3,4,6-tetra-O-galloyl-β-D-glucose (15), 1,2,6-tri-O-galloyl-β-D-glucose (16), 1,3,6-tri-O-galloyl-β-D-glucose (17), gallic acid (18), protocatechuic acid (19), 3,4,5-trimethoxybenzoic acid (20), 2,6-dihydroxyacetophenone (21), 3,3'-di-O-methylellagic acid (22), ellagic acid (23) and esculetin (24) were isolated from Euphorbia lunulata Bge. Their structures were determined by spectroscopic analysis. Isolated hydrolysable tannins, flavonoids, and flavonol galactopyranoside gallates showed significant inhibition of the differentiation of 3T3-L1 preadipocytes and triglyceride accumulation in maturing adipocytes, and nitric oxide production in RAW 264.7 cells.     

Unsaturated 1,2-amino alcohols and ethers from aziridines and organolithiums

Organolithium-induced ring-opening of aziridines of 2,5-dihydrofuran (5 and 8) and 1,4-dimethoxybut-2-ene (16, 17 and 23) gives 3-substituted 2-aminobut-3-en-1-ols 9-15 and amino ethers 18-20 and 24-26.     

Prolyl endopeptidase inhibitory activity of fourteen Kampo formulas and inhibitory constituents of Tokaku-joki-to

Prolyl endopeptidase (PEP, EC 3.4.21.26) is an enzyme playing a role in the metabolism of proline-containing neuropeptides which have been suggested to be involved in learning and memory processes. In screening for PEP inhibitors from fourteen traditional Kampo formulas, we found that Tokaku-joki-to shows a significant inhibitory activity. Examination of the constituents of the Kampo formula resulted in the isolation of two new compounds, cis-3,5,4'-trihydroxystilbene 4'-O-beta-D-(6-O-galloyl)glucopyranoside (10) and 4-(4-hydroxyphenyl)-2-butanone 4'-O-beta-D-(6-O-galloyl-2-O-cinnamoyl)glucopyranoside (16), along with twenty-five known compounds, cinnamic acid (1), protocatechuic acid (2), gallic acid (3), torachrysone 8-O-beta-D-glucoside (4), emodin (5), emodin 8-O-beta-D-glucoside (6), 3,5,4'-trihydroxystilbene 4'-O-beta-D-glucopyranoside (7), 3,5,4'-trihydroxystilbene 4'-O-beta-D-(2-O-galloyl)glucopyranoside (8), 3,5,4'-trihydroxystilbene 4'-O-beta-D-(6-O-galloyl)glucopyranoside (9), 4-(4-hydroxyphenyl)-2-butanone 4'-O-beta-D-glucopyranoside (11), isolindleyin (12), lindleyin (13), 4(4-hydroxyphenyl)-2-butanone 4'-O-beta-D-(2,6-di-O-galloyl)glucopyranoside (14), 4-(4-hydroxyphenyl)-2-butanone 4'-O-beta-D-(2-O-galloyl-6-O-cinnamoyl)glucopyranoside (15), 1-O-galloylglucose (17), 1,2,6-tri-O-galloylglucose (18), gallic acid 4-O-beta-D-(6-O-galloyl)glucopyranoside (19), liquiritigenin (20), liquiritigenin 4'-O-beta-D-glucoside (21), liquiritigenin 7,4'-diglucoside (22), liquiritigenin 4'-O-beta-D-apiofuranosyl-(1-->2)-beta-D-glucopyranoside (23), licuroside (24), (-)-epicatechin (25), (-)-epicatechin 3-O-gallate (26) and (+)-catechin (27). Among these compounds, twelve (7-10, 14-16, 18, 19, 24-26) showed noncompetitive inhibition with an IC50 of 22.9, 3.0, 14.9, 2.8, 10.5, 0.69, 8.2, 0.44, 9.39, 26.5, 28.1 and 0.052 microM, respectively.     

Inhibitory effects of constituents from Morus alba var. multicaulis on differentiation of 3T3-L1 cells and nitric oxide production in RAW264.7 cells

A new arylbenzofuran, 3',5'-dihydroxy-6-methoxy-7-prenyl-2-arylbenzofuran (1), and 25 known compounds, including moracin R (2), moracin C (3), moracin O (4), moracin P (5), artoindonesianin O (6), moracin D (7), alabafuran A (8), mulberrofuran L (9), mulberrofuran Y (10), kuwanon A (11), kuwanon C (12), kuwanon T (13), morusin (14), kuwanon E (15), sanggenon F (16), betulinic acid (17), uvaol (18), ursolic acid (19), β-sitosterol (20), oxyresveratrol 2-O-β-D-glucopyranoside (21), mulberroside A (22), mulberroside B (23), 5,7-dihydroxycoumarin 7-O-β-D-glucopyranoside (24), 5,7-dihydroxycoumarin 7-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranoside (25) and adenosine (26), were isolated from Morus alba var. multicaulis Perro. (Moraceae). Their structures were determined by spectroscopic methods. The prenyl-flavonoids 11-14, 16, triterpenoids 17,18 and 20 showed significant inhibitory activity towards the differentiation of 3T3-L1 adipocytes. The arylbenzofurans 1-10 and prenyl-flavonoids 11-16 also showed significant nitric oxide (NO) production inhibitory effects in RAW264.7 cells.     

A tightly coupled linear array of perylene, bis(porphyrin), and phthalocyanine units that functions as a photoinduced energy-transfer cascade

We have prepared a linear array of chromophores consisting of a perylene input unit, a bis(free base porphyrin) transmission unit, and a free base phthalocyanine output unit for studies in artificial photosynthesis and molecular photonics. The synthesis involved four stages: (1) a rational synthesis of trans-AB2C-porphyrin building blocks each bearing one meso-unsubstituted position, (2) oxidative, meso,meso coupling of the zinc porphyrin monomers to afford a bis(zinc porphyrin) bearing one phthalonitrile group and one iodophenyl group, (3) preparation of a bis(porphyrin)-phthalocyanine array via a mixed cyclization involving the bis(free base porphyrin) and 4-tert-butylphthalonitrile, and (4) Pd-mediated coupling of an ethynylperylene to afford a perylene-bis(porphyrin)-phthalocyanine linear array. The perylene-bis(porphyrin)-phthalocyanine array absorbs strongly across the visible spectrum. Excitation at 490 nm, where the perylene absorbs preferentially, results in fluorescence almost exclusively from the phthalocyanine (phi(f) = 0.78). The excited phthalocyanine forms with time constants of 2 ps (90%) and 13 ps (10%). The observed time constants resemble those of corresponding phenylethyne-linked dyads, including a perylene-porphyrin (< or = 0.5 ps) and a porphyrin-phthalocyanine (1.1 ps (70%) and 8 ps (30%)). The perylene-bis(porphyrin)-phthalocyanine architecture exhibits efficient light-harvesting properties and rapid funneling of energy in a cascade from perylene to bis(porphyrin) to phthalocyanine.