尾式酪氨酸锌卟啉的合成及其非线性光学和热力学性质研究

报道了一种新型尾式酪氨酸锌卟啉(p-(L-Tyr)NC₂H₄OTPPZn)的合成及表征，围绕该化合物进行了非线性光学及热力学性质研究。样品在激光作用下，在一定波长范围内显示出了非常强烈的反饱和吸收行为。对该化合物与3对氨基酸甲酯客体的轴向配位热力学性质作了研究，从热力学数据和圆二色光谱探讨了与不同客体配位能力的差异。     

单体卟啉和二聚体卟啉的合成及其三阶光学非线性的研究

合成了几种卟啉单体和卟啉二聚体, 并测定了它们的三阶光学非线性的吸收系数(β)、折射率(n₂)以及极化率(χ⁽³⁾), 对比研究了卟啉周边取代基及桥连基团的不同对三阶光学非线性的影响. 实验结果表明非线性极化率随卟啉大环电子云密度的增加而增大.     

Synthesis and Photovoltaic Properties of the Copolymers Based on Carbazole with Tetrathiophene Porphyrin Side Chains Linked by a Flexible Alkyl‐interval

Four copolymers (XP10, XP11, XP12 and XP13) based on diketopyrrolopyrrole (DPP) and carbazole units with tetrathiophene porphyrin (TTP) side chains linked by a flexible alkyl‐interval were designed and synthesized. The effects of the introduction of TTP on the optical and electrochemical properties, the morphology, the mobility and the photovoltaic performance of copolymers were systematically studied. The results revealed that XP11 with a TTP/DPP ratio of 2/8 possessed the best performances, i.e., broad absorption spectra, balanced hole/electron mobility and suitable microphase separation. After optimizing via solution vapor annealing, the organic solar cell devices based on XP11 and PC₇₁BM showed the best power conversion efficiency of 5.11% with a short‐circuit current density (J_sc) of 10.36 mA·cm^–2, an open‐circuit voltage (V_oc) of 0.77 V, and a fill factor (FF) of 0.64.     

Synthesis and Optical Properties of Dendronized Porphyrin Polymers

Summary: A novel kind of dendronized porphyrin polymers was synthesized by Sonogashira coupling of diethynyl‐functionalized porphyrin monomers and diiodo‐functionalized macromonomers bearing Fréchet‐type dendrons. The encapsulation of red‐light‐emitting porphyrin‐containing conjugated backbones into dendronized polymers can not only reduce the aggregation of polymer backbones and the self‐quenching of their fluorescence but also endow the porphyrin polymers with good solubility. We also report the optical and electrochemical properties of the porphyrin‐containing dendronized polymers.

Synthesis of a novel kind of dendronized porphyrin polymers by Sonogashira coupling of diethynyl‐functionalized porphyrin monomers and diiodo‐functionalized dendritic macromonomers.     

具有推拉电子结构卟啉染料的合成及其在染料敏化太阳能电池中的应用

将N,N’-二-(9,9’-二己基芴)胺作为电子供体引入具有推拉电子结构的卟啉染料中,设计合成了2个新的染料敏化太阳能电池(DSSCs)敏化剂WP-1和WP-2。利用核磁共振氢谱和高分辨质谱对染料结构进行了表征。测试了染料的紫外-可见吸收光谱。将其应用于染料敏化太阳能电池中,在模拟太阳光(100×10-3W/cm2)照射下,染料WP-1和WP-2敏化电池的能量转换效率分别达到了4.01%和7.07%。WP-2敏化的电池封装后经自然光照射500 h后,光电效率仍能维持在初始效率的98%以上。说明N,N’-二-(9,9’-二己基芴)胺作为电子供体,很适合推拉电子结构的卟啉染料。不仅丰富了用于卟啉染料的电子供体的种类,也为进一步将二芴胺衍生物引入到卟啉染料中的研究奠定了基础。     

基于苯并噻二唑的菁染料敏化剂的合成与光伏性能研究

两个新型的基于三苯胺苯并噻二唑的菁染料(I～II)通过含有该单元的苯并[e]吲哚啉乙醛和1,1,2-三甲基-3-丁 基-5-羧基-3H-吲哚碘盐的Knoevenagel缩合反应合成, 其结构用核磁和高分辨质谱进行了表征|对两个菁染料敏化剂的光物理、电化学性能和太阳能电池的光伏性能进行了系统研究. 在AM1.5G标准光源下, 两个染料的最高入射单色光子-电子转化效率值(IPCE值)均超过57%, 其光电转换效率分别为2.59%和3.28%.     

Effects of Donor and Acceptor on Optoelectronic Performance for Porphyrin Derivatives: Nonlinear Optical Properties and Dye-sensitized Solar Cells

Typical asymmetric donor-π-bridge-acceptor(D-π-A) zinc porphyrin dyes have been synthesized, and further modified by reacting the ethynyl groups of them with click reagent through a formal [2+2] click reaction. The electronic interaction between the push and pull electronic groups and the click reaction process were investigated by UV-Vis absorption spectroscopy. The nonlinear optical(NLO) properties of the dyes were studied by the Z-scan technique and clearly reverse saturable absorption to saturable absorption(RSA-SA) transition could be observed through click reaction of the dyes with TCNE. Furthermore, the photovoltaic properties of these porphyrin dyes were reaso- nably explained by the J-V curve fitting based on the equivalent-circuit model as well as the comparison between the absorption and incident-photon-to-current-conversion efficiency(IPCE) spectra. Besides, these dyes with different donors or acceptors could self-assembly into different microstructures by phase transfer methodology.     

新型吡啶基修饰的尾式卟啉的合成及性质

报道了一种新型尾式锌卟啉(o-PyOC₆H₁₂OTPPZn)的合成及表征, 采用紫外-可见光谱滴定法对该化合物与5种吡啶类小分子间的轴向配位反应的热力学性质进行了研究. 轴配体系的热力学数据显示, 5种吡啶类配体的平衡常数按K(4-MePy)>K(Py)>K(3-MePy)>K(2,4,6-triMePy)>K(2-MePy)依次减小, 吡啶类小分子对主体的配位能力按4-MePy>Py>3-MePy>2,4,6-triMePy>2-MePy依次减弱, 同时分子模拟的理论研究得到了与实验完全一致的结果. 通过Z-扫描实验对该化合物的非线性光学性质的研究表明, 该样品具有较强的反饱和吸收特征.     

Theoretical Studies on the Absorption Spectra and Intramolecular Charge Transfer of Push-pull Zinc Porphyrin Dyes for Dye-sensitized Solar Cells

The electronic structures, absorption spectra and intramolecular charge transfer properties of five push-pull zinc porphyrin analogs with different donor group and π bridge have been investigated by density functio- nal theory(DFT) and TD(time-dependent)-DFT approach. The results show that the asymmetrical substituted diphenylamine group is favorable to the Q-band absorption of porphyrin dyes. The absence of the acetylenic bond in the π bridge part leads to the result that the B-band and the Q-band are blue-shifted and their absorption strength become weaker compared with that containing acetylenic bond, respectively. The introduction of the benzothiadiazole into the π bridge improves the intramolecular charge transfer.     

一种天线分子与卟啉染料自组装在染料敏化太阳能电池中的应用

以卟啉分子H2-pTCPP作为基础染料,通过配位自组装的方法将天线分子S3修饰到染料结构中。结果表明经天线分子修饰后染料敏化太阳能电池器件的整体性能得到了极大的改善。天线效应有效地提高了器件的光子捕获能力,光电流得到了显著的提高,并且电荷复合行为也得到了明显的抑制。基于H2-pTCPP的电池器件显示了1.18%的转换效率,而经过天线分子修饰后的Mn-pTCPP+S3显示了2.64%的转换效率,性能提高了1.2倍。     

新型三卟啉醚类配体的合成及其光学性能

以吡咯,对羟基苯甲醛和对甲氧基苯甲醛为原料,经alder反应制得单羟基卟啉(1);1与1,3,5-三(溴甲烷)苯连接合成了一种新型的三卟啉醚类配体(3),其结构经1H NMR,FT-IR和FAB-MS表征。通过UV-Vis,荧光光谱和拉曼光谱研究了3的光学性能。结果表明:3的λmax位于425,520,550,650nm;λem位于650,718nm;荧光量子产率为0.012 9。     

N,N-二苯基取代的芳炔化合物的合成及光伏性能

以简单原料出发,通过Sonogashira偶联反应和三甲基硅基(TMS)的保护与脱保护,合成了一系列N,N-二苯基取代的芳炔化合物SC1～SC5.这类化合物是以N,N-二苯基为电子给体,羧基为电子受体,芳香炔体系为共轭桥的染料.将化合物SC5吸附到TiO2膜上制备成有机染料敏化太阳能电池,在AM 1.5,100 mW/cm2的模拟太阳光下,电池的光电转换效率(IPCE)值最大达到64%,而且在350～580 nm的范围内都可达到50%以上.电池的短路电流密度Jsc=8.0mW/cm2,开路电压Voc=0.75 V,填充因子为FF=0.70,总光电转换效率η=4.2%.     

新型卟啉及其锌配合物的合成与性质研究

设计合成了一种新型的不对称卟啉(5,10,15-三苯基-20-{4-[6′-(4″-o-亚水杨基)-苯亚胺基]己氧基}苯基卟啉)及其锌配合物,并用¹H NMR、质谱及紫外-可见光谱进行表征。采用紫外-可见光谱滴定法,对锌卟啉与4种咪唑类小分子间的轴向配位反应热力学性质的研究表明：反应为放热、熵增加过程,4种咪唑类配体对锌卟啉的配位平衡常数按K^Θ(2-MeIm)>K^Θ(N-MeIm)>K^Θ(2-Et-4-MeIm)>K^Θ(Im)顺序依次减小。运用Z-扫描技术研究了新型卟啉及其锌配合物的非线性光学性质。     

Novel Zinc Porphyrin Sensitizers for Dye‐Sensitized Solar Cells: Synthesis and Spectral,Electrochemical, and Photovoltaic Properties

Novel meso‐ or β‐derivatized porphyrins with a carboxyl group have been designed and synthesized for use as sensitizers in dye‐sensitized solar cells (DSSCs). The position and nature of a bridge connecting the porphyrin ring and carboxylic acid group show significant influences on the spectral, electrochemical, and photovoltaic properties of these sensitizers. Absorption spectra of porphyrins with a phenylethynyl bridge show that both Soret and Q bands are red‐shifted with respect to those of porphyrin 6 . This phenomenon is more pronounced for porphyrins 3 and 4 , which have a π‐conjugated electron‐donating group at the meso position opposite the anchoring group. Upon introduction of an ethynylene group at the meso position, the potential at the first oxidation alters only slightly whereas that for the first reduction is significantly shifted to the positive, thus indicating a decreased HOMO–LUMO gap. Quantum‐chemical (DFT) results support the spectroelectrochemical data for a delocalization of charge between the porphyrin ring and the amino group in the first oxidative state of diarylamino‐substituted porphyrin 5 , which exhibits the best photovoltaic performance among all the porphyrins under investigation. From a comparison of the cell performance based on the same TiO₂ films, the devices made of porphyrin 5 coadsorbed with chenodeoxycholic acid (CDCA) on TiO₂ in ratios [ 5 ]/[CDCA]=1:1 and 1:2 have efficiencies of power conversion similar to that of an N3 ‐based DSSC, which makes this green dye a promising candidate for colorful DSSC applications.     

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.     

新型噻咯共轭聚合物的合成及其光伏性能

噻咯(silole)是一类含硅的五元环二烯, 具有很好的电子亲和力、独特的聚集态诱导发光性质和优良的电致发光性能. 研究者发现将噻咯结构单元引入分子主链中, 能够获得具有特殊光电性能的聚合物材料. 本工作合成两种2,5位为二噻吩苯并噻二唑的新型噻咯单体, 通过与芴或硅芴双硼酸酯Suzuki偶联聚合, 制备四种主链型D-A(推-拉电子结构)共聚物PF-HSTBT, PF-HOSTBT, PSiF-HSTBT和PSiF-HOSTBT. 研究表明, 四种聚合物具有较好的吸收, 光学带隙均小于1.71 eV. 电化学分析测得四种聚合物的HOMO能级均小于-5.29 eV, 通过光学带隙计算得LUMO能级均高于-3.61 eV. 以四种聚合物分别作为电子给体材料, PC₆₁BM为受体材料, 制备了聚合物太阳能电池器件(PSCs). 由于聚合物PF-HOSTBT、PSiF-HOSTBT中的己氧基空间位阻较大, 分子平面规整性较差, 其最高光电转换效率分别为0.62%、0.83%; 而己基的空间位阻较小, 分子堆积紧密, 聚合物PF-HSTBT, PSiF-HSTBT的光伏性能较优, PSCs的最高光电转换效率分别为1.18%, 1.2%.     

形貌可控卟啉材料的合成及光电性质

通过自组装方法制备了一种卟啉材料,并通过调节溶液pH值实现了对其形貌的可控。 当pH值较低时形成卟啉棒状结构;当pH值较高时形成卟啉叶片状结构。 利用紫外、红外和X衍射仪等多种表征方法对其结构和性质进行了表征。 结果表明,在无机酸的作用下,卟啉分子通过π-π、静电作用形成一维结构的J-聚集体;当pH值增加时,氢键的作用占主要作用形成二维片状结构。 将此卟啉棒状材料构筑微纳米器件,测试其光电性能,表明对可见光有很好的响应。 这种具有光电响应的卟啉材料有望成为微纳电子器件的光电元件。     

Nonlinear Optical Properties of Porphyrin Derivatives with Electron‐donating or Electron‐withdrawing Substituents

To investigate photoelectric properties of meso‐extended porphyrin derivatives with electron‐donating or electron‐withdrawing substituents, a series of functionalized porphyrin materials have been designed and synthesized by Suzuki coupling reaction. The meso‐extended structures were fully characterized by ¹H NMR, IR spectroscopy and mass spectrometry. The photophysical properties of porphyrin derivatives were carefully examined by UV‐Visible and fluorescence spectra, and the solvatochromic effect was observed and discussed. In particular, Z‐scan technique was employed to characterize the third‐order nonlinear optical (NLO) properties of the products such as nonlinear absorption and refraction, the third‐order nonlinear refractive indexes (??⁽³⁾‐value) of these porphyrin derivatives achieved 3.9×10^?12 esu. In addition, the compounds could be self‐assembled into highly organized morphologies through phase‐exchange method. All the results indicated that the discotic materials have the potential for optoelectronic applications.     

A novel self-assembly based on double-layer zinc porphyrin sensitizers in supramolecular solar cell

Two new self-assemblies based on zinc porphyrin dyes ZnPx-ZnPA (x?=?1, 2) were synthesized and used for dye-sensitized solar cells. Capping layer dyes consist of zinc porphyrin (ZnP) as core unit and carbazole (P1), phenothiazine (P2) as electron-donating group. The dye ZnPA contains carboxylic group as an anchor porphyrin with upper dyes (denoted as ZnP1 and ZnP2) formed dyads by coordination bonds of Zn-to-ligand self-assembled devices. The assembly modes were also verified by transmission electron microscopy (TEM). The influence of the upper porphyrins on molecular structure as well as photovoltaic performance was investigated via photophysical and electrochemical studies and calculations. With addition of the phenothiazine unit, the ZnP2-ZnPA possesses better light-harvesting capability with a significantly red-shifted Q-band. The photoelectrochemical efficiencies for ZnP2-ZnPA are better than those of ZnP1-ZnPA ascribed to larger J_sc and V_oc.

     

卟啉化合物在有机染料敏化太阳能电池中的应用研究

卟啉化合物具有共轭的平面结构、良好的电子缓冲性和光电磁性,特别在可见光区和近红外区域具有优越的光捕获特性。近年来,卟啉类化合物以其优异的特性在有机太阳能电池领域,尤其是染料敏化太阳能电池中得到了广泛的应用研究。人们通过对卟啉分子进行改性来提高相应的太阳能电池效率,比如增加分子的共轭度、在分子上引入长烷基链、引入功能化小...