Meso-四（4-（N-咔唑）丁烷氧苯基）卟啉稀土金属配合物的合成及光电性质

本文设计合成了未见文献报道的meso—N（4-（N-咔唑）丁烷氧苯基）卟啉（1）及其稀土金属配合物（Ln=Sm（2）,Eu（3）,Tb（4）,Dy（5））．通过核磁共振氢谱、紫外．可见吸收光谱、元素分析和红外光谱对稀土金属卟啉配合物进行了表征,并研究了卟啉样品的荧光性质和表面光电压性质．结果表明,受无辐射跃迁等因素的影响,卟啉1～5的荧光强度和荧光量子效率依次减小．在无外加电场的情况下,稀土金属配合物2～5的表面光电压强度变化与荧光强度变化呈现相反的规律,充分表明荧光发射与表面光电压的相互竞争过程．不同性质的电场对金属卟啉配合物的电荷分离影响显著,在正电场和无外加电场情况下,配合物2～5的表面光电压信号强度依次增加．     

载有卟啉的介孔SBA-15表面光电压的性质研究

用表面光电压谱(SPS)和场诱导表面光电压谱(FISPS)技术对比研究了卟啉和介孔SBA-15及载有卟啉的介孔SBA-15的表面光伏特性.固载后同时显示了卟啉和介孔的光电压性质,但是光电压响应强度减弱,这是因为卟啉和介孔之间发生了电子传递的缘故.在外电场诱导下,它们的光伏响应强度随外加正电场光伏响应强度的增加而增强,随外加负电场光伏响应强度的增加而减弱.而装载后的SBA-15在334和425 nm处的光伏响应信号随外加电场的变化而有不同的变化.     

Meso-四(对-酰氧基苯基)钴、镍卟啉液晶的性质

合成了6个系列12个四(对-酰氧基苯基)卟啉钴和镍配合物, 用元素分析、红外光声光谱、紫外可见光谱、质谱以及核磁共振氢谱等对其结构进行了表征, 同时利用DSC、偏光显微镜、循环伏安和表面光电压谱对其液晶性能、电化学性质、荧光性质以及表面光伏特性进行了研究. 结果表明, 有9种配合物具有液晶性质, 为六角柱状结构, 均为具有较强荧光发射性质的p型半导体. 相变温度最低的是四(对-十八酰氧基苯基)卟啉镍, 为-22.54℃.     

以反丁烯二酰氯桥联的10,15,20-三（对-氯代苯基）卟啉二联体及其配合物的合成与性质研究

用5-（对-羟基苯基）-10,15,20-三（对-氯代苯基）卟啉为原料合成了以反丁烯二酰氯桥连的10,15,20-三（对-氯代苯基）卟啉二联体及其Zn,Cu,Co,Mn配合物,并用红外光谱、拉曼光谱、紫外光谱、质谱、核磁共振谱对其结构进行了表征.利用分子荧光光谱和表面光电压对其光学性质进行了研究.     

不对称酰胺基卟啉及其锌配合物的合成,表征及光谱研究

以CH2Cl2为溶剂,通过5-(4-氨基)苯基-10,15,20-三苯基卟啉(MATPP)与异烟酸直接反应得到一种不对称酰胺基卟啉配体(H2P),并合成了其锌配合物(ZnP),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.同时,结合光谱法初步研究了卟啉的自聚合性质.研究表明,紫外-可见光谱显示了卟啉的J-聚合特征,荧光量子产率由于自聚合而降低.     

四甲基-四乙基钯卟啉的表面光伏特性研究

合成了1,3,5,7-四甲基-2,4,6,8-四乙基卟啉(TMTEP)及其钯络合物(PdTMTEP),并利用表面光电压谱(SPS)和场诱导表面光电压谱(FISPS)技术对它们的表面光伏特性进行了研究.TMTEP有较强的荧光发射,而PdTMTEP以磷光辐射为主,其光伏响应强度比TMTEP的强得多;在外电场诱导下,PdTMTEP的Soret带与Q带的光伏响应强度随外加正电场光伏响应强度的增加而增强,随外加负电场光伏响应强度的增加而减弱,并且在680,750nm处出现两个新的光伏响应带,这两个光伏响应带与极化子跃迁有关.     

Meso位单取代卟啉及其配合物的合成、表征和光谱性质（英文）

设计合成了一系列新型的meso位N,N-二甲氨基苯基或N-苯基咔唑基单取代卟啉(5a~c)及其锌配合物(6a~c),用高分辨质谱、~1H NMR、紫外-可见光谱及X射线单晶衍射方法等对结构进行了表征;研究了卟啉化合物及其配合物的热稳定性及荧光性质。结果表明,这些卟啉化合物及其锌配合物在400~410 nm之间具有强的吸收且具有很好的热稳定性,荧光量子产率在0.05~0.09;另外还分析了meso位不同取代基对光谱性质的影响。     

5-氟尿嘧啶卟啉锰/锌配合物的合成、光电性质及抗癌活性

合成了新型5-氟尿嘧啶修饰的自由卟啉5-(2-(5-氟尿嘧啶-3-基)乙氧基苯基)-10,15,20-三苯基卟啉(L)及其锰配合物(MnL)和锌配合物(ZnL)。通过紫外-可见光谱、红外光谱、核磁共振氢谱及高分辨质谱等手段进行了结构表征。研究了它们的荧光性质和电化学性质;应用标准磺酰罗丹明B法(SRB法)测试了目标化合物对人肺癌细胞株A549、人肝癌细胞株Bel-7402和人结肠癌细胞株HCT-8生长的抑制活性。结果表明:相同实验条件下,不同金属离子对配合物的荧光强度存在较大影响:锌配合物具有荧光猝灭的性质,而锰配合物未能观察到明显的荧光发射光谱;与自由卟啉和锌配合物相比,锰配合物除卟啉环发生氧化还原反应外,Mn~(2+)自身也发生了氧化还原反应;抗癌活性测试显示锰配合物较其他2种化合物有较好的抗癌活性。     

反丁烯二酰基桥连的带不同取代基的卟啉二联体的合成与性质

合成了反丁烯二酰基桥连的3种带不同取代基的卟啉二联体, 通过红外光谱, 紫外-可见光谱, 核磁共振波谱和质谱对化合物的结构进行了确认, 并研究了二联体的表面光电压谱, 荧光光谱和激光拉曼光谱的变化. 结果表明, 取代基的类型对卟啉二联体分子的荧光量子产率有显著影响, 带供电子基团的甲氧基增强了荧光量子产率, 而带吸电子基团的氯则降低了荧光量子产率, 并且吸电子基团的氯比供电子基团的甲氧基对荧光的影响更大. 取代基的电子效应对卟啉二联体的荧光性和激光拉曼光谱有较大影响.     

镱(Ⅲ)卟啉配合物的合成、结构表征和近红外光谱研究

合成了5个meso-位和β-位具有不同取代基的Yb(Ⅲ)卟啉配合物(2a~2e), 并对其结构进行了表征; 研究了配合物的可见光谱和近红外光谱性质, 测得了相关的量子产率和荧光寿命. 研究结果表明, 此类中性单核Yb(Ⅲ)卟啉配合物由于Yb³⁺的存在, 导致卟啉配体发生π→π*跃迁, 并将吸收的可见光能量传递给Yb³⁺的激发态, 使得配合物在近红外光区有很强的发光, 且meso-位为供电子基团的Yb(Ⅲ)卟啉配合物的发光效率比含吸电子基团的Yb(Ⅲ)卟啉配合物高, 而β-位溴化的Yb(Ⅲ)卟啉配合物的发光效率较差.     

新型尾式组氨酸卟啉的合成及性质

设计并合成了新型尾式氨基酸卟啉5-(Trt-组氨酸酰胺基苯基)-10,15,20-三苯基卟啉(Trt-His-NH2-TPP,1)及其金属卟啉配合物(Zn,Co,Fe,Mn,分别标记为2～5).通过元素分析、核磁共振氨谱、质谱、紫外-可见光谱和红外光谱等对化合物进行了表征,研究了它们的荧光性质,并通过理论模拟研究了其最...     

5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌配合物的合成表征

设计合成了5种未见文献报道的5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌金属配合物,并用IR,UV-Vis,1H NMR,元素分析以及XPS对其组成和结构进行了表征,研究了这10种酰胺基系列卟啉化合物的拉曼光谱和荧光光谱的变化.结果显示链长对荧光和拉曼光谱没有明显影响,其取代基效应基本相同,配体的荧光强度强于锌配合物的荧光强度.在拉曼光谱中,由于卟啉分子平面的对称性由D2h变为D4h群及其锌离子d轨道的电子效应,卟啉配体和锌配合物之间的拉曼光谱有很大差别.     

Ultrafast spectroscopy of free-base N-confused tetraphenylporphyrins

The photophysical characterization of the two tautomers (1e and 1i) of 5,10,15,20-tetraphenyl N-confused free-base porphyrin, as well as the tautomer-locked 2-methyl 5,10,15,20-tetraphenyl N-confused free-base porphyrin, was carried out using a combination of steady state and time-resolved optical techniques. N-Confused porphyrins, alternatively called 2-aza-21-carba-porphyrins or inverted porphyrins, are of great interest for their potential as building blocks in assemblies designed for artificial photosynthesis, and understanding their excited-state properties is paramount to future studies in multicomponent arrays. Femtosecond resolved transient absorption experiments reveal spectra that are similar to those of tetraphenylporphyrin (H2TPP) with either Soret or Q-band excitation, with an extinction coefficient for the major absorbing band of 1e that was about a factor of 5 larger than that of H2TPP. The lifetime of the S1 state was determined at a variety of absorption wavelengths for each compound and was found to be consistent with time-resolved fluorescence experiments. These experiments reveal that the externally protonated tautomer (1e) is longer lived (tau = 1.84 ns) than the internally protonated form (1i, tau = 1.47 ns) by approximately 369 ps and that the N-methyl N-confused porphyrin was shorter lived than the tautomeric forms by approximately 317 ps (DMAc) and approximately 396 ps (benzene). Steady-state fluorescence experiments on tautomers 1e and 1i and the N-methyl analogues corroborate these results, with fluorescence quantum yields (Phi(Fl)) of 0.046 (1e, DMAc) and 0.023 (1i, benzene), and 0.025 (DMAc) and 0.018 (benzene) for the N-methyl N-confused porphyrin. The lifetime and quantum yield data was interpreted in terms of structural changes that influence the rate of internal conversion. The absorption and transient absorption spectra of these porphyrins were also examined in the context of DFT calculations at the B3LYP/6-31G(d)//B3LYP/3-21G(d) level of theory and compared to the spectra/electronic structure of H2TPP and tetraphenyl chlorin.     

5,10,15,20-四(对-十四酰亚胺基苯基)卟啉及其锰、锌配合物的合成及性质

合成了5,10,15,20-四(对-十四酰亚胺基苯基)卟啉配体(TMPPH2)及其锰、锌金属配合物(TMPPMnCl, TMPPZn), 并通过紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等技术对化合物的结构加以确认, 研究了配体和配合物的拉曼光谱、光电子能谱和荧光光谱的变化及电化学性质. 结果表明, 配体和配合物的紫外光谱、红外光谱、拉曼光谱、荧光光谱及光电子能谱都有很大区别, 锰配合物的循环伏安曲线与配体和锌配合物不同, 除了卟啉环发生氧化还原外, 还发生了金属离子的氧化还原反应.     

Porphyrin, phthalocyanine and porphyrazine derivatives with multifluorenyl substituents as efficient deep-red emitters

The synthesis and photophysical properties are described for a series of porphyrin, phthalocyanine and pyrazinoporphyrazine derivatives which bear four or eight peripheral fluorenyl substituents as antennae. Representative examples are 5,10,15,20-tetra(9,9-dihexyl-9H-fluoren-2-yl)porphyrin (2), 5,10,15,20-tetrakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]porphyrin (3), 2,3,9,10,16,17,23,24-octakis(9,9-dihexyl-9H-fluoren-2-yl)-29H,31H-phthalocyanine (8) and 2,3,9,10,16,17,23,24-octakis[4-(9,9-dihexyl-9H-fluoren-2-yl)phenyl]-29H,31H-tetrapyrazinoporphyrazine (9). Palladium-mediated Suzuki-Miyaura cross-coupling reactions have been key steps for attaching the substituents. The compounds are deep-red emitters: lambda(max)(em)=659 (3), 737 (8) and 684 nm (9). Their absorption and emission spectra, their fluorescence lifetimes and quantum yields are correlated with the structures of the macrocycles and the substituents. The solution fluorescence quantum yields of porphyrin derivatives substituted with fluorene (2-4) and terphenyl substituents (7) (Phi(f)=0.21-0.23) are approximately twice that of tetraphenylporphyrin. For phthalocyanine derivative 8, Phi(f) was very high (0.88). Specific excitation of the fluorene units of 8 produced emission from both of them (lambda(max)=480 nm) and also from the phthalocyanine core (lambda(max)=750 nm), indicating a competitive rate of energy transfer and radiative decay of the fluorenes. Organic light-emitting devices (OLEDs) were made by spin-coating techniques by using a polyspirobifluorene (PSBF) copolymer as the host blended with 3 (5 wt. %) in the configuration ITO/PEDOT:PSS/PSBF copolymer:3/Ca/Al. Deep-red emission (lambda(max)=663 nm; CIE coordinates x=0.70, y=0.27) was observed with an external quantum efficiency of 2.5 % (photons/electron) (at 7.5 mA cm(-2)), a low turn-on voltage and high emission intensity (luminance) of 5500 cd m(-2) (at 250 mA/ m(2)).     

Photoinduced intermolecular and intramolecular actions between eosin and porphyrin

Two dyads of eosin and porphyrin linked with a semi-rigid (-CH2phCH2-) or flexible (-(CH2)4-) bridge and their reference model compounds were synthesized and characterized The intermoleccular interaction and intramolecular photoinduced singlet energy transfer and electron transfer were studied by their absorp tion spectra,fluorescence emission,excitation spectra and fluorescence lifetime The model compounds,ethyl ester of eosm (EoEt) and porphyrin (PorEt),could form complexes in the ground state.When the eosin moieties in dyads were excited,they could transfer some singlet energy to the porphyrins; in the meantime,they could also ndsce electron transfer between two chromophores.Exciting the porphyrin moieties in dyads could induce electron transfer from eosin moieties to porphyrin moieties.The efficiencies (EnT,ET) and rate constants (kEnT,kET) were related to the polarity of solvents and mutual orientation of the two chromophores in dyads.     

Equilibrium, photophysical, photochemical, and quantum chemical examination of anionic mercury(II) mono- and bisporphyrins

Mercury(II) ion and 5,10,15,20-tetrakis(parasulfonato-phenyl)porphyrin anion can form 1:1, 2:2, and 3:2 (metal ion/porphyrin) out-of-plane (OOP) complexes, from which Hg2P2(8-) has not been identified until now. Identification of this species significantly promoted the confirmation of the composition and the precise elucidation of the equilibrium of Hg3P2(6-). Since the formation of each complex is too fast, their kinetic behavior was studied from the side of dissociation. The rate-determining step in dissociations, as well as in the formation of the 2:2 complex, that is, the dimerization of 1:1 complex, proved to be virtually first-order under these conditions, while the consecutive formations of HgP(4-) and Hg3P2(6-) are second-order reactions. The equilibria can be spectrophotometrically investigated because the Soret- as well as the Q-absorption bands of the free-base ligand are more and more red-shifted in the series of 1:1, 2:2, and 3:2 complexes, and the split of Q-bands disappears as the singlet-1 excited states become degenerate; in the case of bisporphyrins, the bands broaden, especially in the longer-wavelength region of the spectra. The quantum yield and the lifetime of S1-fluorescence from the macrocycle is decreased by the insertion of a mercury(II) ion due to distortion, and in bisporphyrins the luminescence totally ceases because their more complicated structure promotes other ways of energy dissipation. The lifetime of the triplet excited-state is also reduced by metalation. The transient absorption measured upon excitation of Hg3P2(6-) probably originates from Hg2P2(8-) formed by efficient photodissocation during the laser pulse. This photoinduced dissociation is characteristic to out-of-plane complexes, but in metallo-monoporphyrins it needs the energetically higher Soret-excitation; in bisporphyrins, it can take place during irradiation at the longer Q-wavelengths. Investigation of the intramolecular photoredox reactions has proved that for the increased efficiency of the indirect photoinduced LMCT, not the redox potential, but the position of the metal center is responsible. The two orders of magnitude higher photoredux quantum yield for the 3:2 complex, compared to that of the 2:2 species, can be explained by the repulsive effect of the inner mercury(II) ion pushing the other two farther out of the ligand cavity. In bisporphyrins the second excited states are photochemically more reactive than the first ones, while most of the photochemical processes of HgP(4-) originate from the first excited state. According to our quantum chemical calculations, the mercury(II) ion causes the expansion of the porphyrin-cavity; therefore its out-of-plane position is smaller than the value expected based on its ionic radius. In the hitherto unknown 2:2 dimer two 1:1 saucer-shaped monomers are kept together by secondary forces, mostly by pi-pi interaction, but their relative arrangement was not unequivocally determined by the two DFT functionals used. The arrangements with a symmetry axis or plane perpendicular to both rings are not favored; instead, the two monomers are shifted along the porphyrin planes, either in a Hg-P-Hg-P or a Hg-P-P-Hg order. Our time-dependent density functional theory (TD-DFT) calculations indicate that the electronic spectra are not very sensitive to the structure of the dimer, even though the environment of the porphyrin rings is quite different if one of the metal ions is between or outside of both macrocycles. The calculated spectral shifts agree only partially with the experimental data. The TD-DFT calculations suggest that the chromophores are not fully independent in the bisporphyrins and that the observed spectral shift cannot be uniquely assigned to the geometrical distortion of the porphyrin macrocyle.     

Quantum chemical simulation of excited states of chlorophylls, bacteriochlorophylls and their complexes

The present review describes the use of quantum chemical methods in estimation of structures and electronic transition energies of photosynthetic pigments in vacuum, in solution and imbedded in proteins. Monomeric Mg-porphyrins, chlorophylls and bacteriochlorophylls and their solvent 1:1 and 1:2 complexes were studied. Calculations were performed for Mg-porphyrin, Mg-chlorin, Mg-bacteriochlorin, mesochlorophyll a, chlorophylls a, b, c(1), c(2), c(3), d and bacteriochlorophylls a, b, c, d, e, f, g, h, plus several homologues. Geometries were optimised with PM3, PM3/CISD, PM5, ab initio HF (6-31G*/6-311G**) and density functional B3LYP (6-31G*/6-311G**) methods. Spectroscopic transition energies were calculated with ZINDO/S CIS, PM3 CIS, PM3 CISD, ab initio CIS, time-dependent HF and time-dependent B3LYP methods. Estimates for experimental transition energies were obtained from linear correlations of the calculated transition energies of 1:1 solvent complexes against experimentally recorded solution energies (scaling). According to the calculations in five-coordinated solvent complexes the magnesium atom lies out of the porphyrin plane, while in six-coordinated complexes the porphyrin is nearly planar. Charge densities on magnesium and nitrogen atoms were strongly dependent on the computational method deployed. Several dark states of low oscillator strength below the main Soret band were predicted for solvent complexes and chlorophylls and bacteriochlorophylls in protein environment. Such states, though not yet identified experimentally, might serve as intermediate states for excitation energy transfer in photosynthetic complexes. Q(y), Q(x) and Soret transition energies were found to depend on the orientation of the acetyl group and external pressure. A method to estimate site energies and dimeric interaction energies and to simulate absorption and CD spectra of photosynthetic complexes is described. Simulations for the light harvesting complexes Rhodospirillum molischianum, chlorosomes of Chlorobium tepidum and Chloroflexus aurantiacus, and LHC-II of Spinacia oleracea are presented as examples.