- Chiral and achiral basket-handle porphyrins: Short synthesis and stereostructures of these versatile building blocks
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Both, chiral and achiral basket-handle porphyrins were synthesized via a short, reliable, and efficient route in multigram quantities. Standard synthetic protocols such as metalation of the macrocycle, halogenation, and borylation of the porphyrin core or alkyl- and arylation with lithium organyls were successfully adapted. The planar-chiral representatives were resolved into their enantiomers, whose absolute configurations were determined by comparison of experimental CD spectra with TDCAM-B3LYP calculated ones.
- Gehrold, Andreas C.,Bruhn, Torsten,Schneider, Heidi,Radius, Udo,Bringmann, Gerhard
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- Extraction of photogenerated electrons and holes from a covalent organic framework integrated heterojunction
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Covalent organic frameworks (COFs) offer a strategy to position molecular semiconductors within a rigid network in a highly controlled and predictable manner. The π-stacked columns of layered two-dimensional COFs enable electronic interactions between the COF sheets, thereby providing a path for exciton and charge carrier migration. Frameworks comprising two electronically separated subunits can form highly defined interdigitated donor-acceptor heterojunctions, which can drive the photogeneration of free charge carriers. Here we report the first example of a photovoltaic device that utilizes exclusively a crystalline organic framework with an inherent type II heterojunction as the active layer. The newly developed triphenylene-porphyrin COF was grown as an oriented thin film with the donor and acceptor units forming one-dimensional stacks that extend along the substrate normal, thus providing an optimal geometry for charge carrier transport. As a result of the degree of morphological precision that can be achieved with COFs and the enormous diversity of functional molecular building blocks that can be used to construct the frameworks, these materials show great potential as model systems for organic heterojunctions and might ultimately provide an alternative to the current disordered bulk heterojunctions.
- Calik, Mona,Auras, Florian,Salonen, Laura M.,Bader, Kathrin,Grill, Irene,Handloser, Matthias,Medina, Dana D.,Dogru, Mirjam,L?bermann, Florian,Trauner, Dirk,Hartschuh, Achim,Bein, Thomas
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- A Porphyrin-Based Conjugated Polymer for Highly Efficient In Vitro and In Vivo Photothermal Therapy
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Conjugated polymers have been increasingly studied for photothermal therapy (PTT) because of their merits including large absorption coefficient, facile tuning of exciton energy dissipation through nonradiative decay, and good therapeutic efficacy. The high photothermal conversion efficiency (PCE) is the key to realize efficient PTT. Herein, a donor–acceptor (D–A) structured porphyrin-containing conjugated polymer (PorCP) is reported for efficient PTT in vitro and in vivo. The D–A structure introduces intramolecular charge transfer along the backbone, resulting in redshifted Q band, broadened absorption, and increased extinction coefficient as compared to the state-of-art porphyrin-based photothermal reagent. Through nanoencapsulation, the dense packing of a large number of PorCP molecules in a single nanoparticle (NP) leads to favorable nonradiative decay, good photostability, and high extinction coefficient of 4.23 × 104m?1 cm?1 at 800 nm based on porphyrin molar concentration and the highest PCE of 63.8% among conjugated polymer NPs. With the aid of coloaded fluorescent conjugated polymer, the cellular uptake and distribution of the PorCP in vitro can be clearly visualized, which also shows effective photothermal tumor ablation in vitro and in vivo. This research indicates a new design route of conjugated polymer-based photothermal therapeutic materials for potential personalized theranostic nanomedicine.
- Guo, Bing,Feng, Guangxue,Manghnani, Purnima Naresh,Cai, Xiaolei,Liu, Jie,Wu, Wenbo,Xu, Shidang,Cheng, Xiamin,Teh, Cathleen,Liu, Bin
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- Novel Cofacial Porphyrin-Based Homo- and Heterotrimetallic Complexes of Transition Metals
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We present a straightforward and generally applicable synthesis route for cofacially linked homo- and heterotrimetallic trisporphyin complexes. The protocol encompasses synthesising the first aryl-based, trans-o-phenylene trisporphyrin starting from pyrrole and benzaldehyde with an overall yield of 3.6 %. It also allows investigating the respective cis-isomer as the first conformationally restricted planar-chiral trisporphyrin. The free-base ligand was used in subsequent metalation reactions to afford the corresponding homotrimetallic Mn(III)-, Fe(III)-, Ni(II)-, Cu(II)-, Zn(II)- and Pd(II) complexes – additionally, a small adaptation of the protocol resulted in the defined Ni(II)Fe(III)Ni(II) complex in a total yield of 2.3 %. By monitoring Ni(II) insertion into the empty trimeric ligands, we affirmed that the outer porphyrin rings are filled before the internal ring. The molecular species were characterised by 1H NMR, UV-Vis, photoluminescence, IR, MS, CID, and high-resolution IMS measurements.
- Schissler, Christoph,Schneider, Erik K.,Lebedkin, Sergei,Weis, Patrick,Niedner-Schatteburg, Gereon,Kappes, Manfred M.,Br?se, Stefan
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- Selective oxidation of alcohols by porphyrin-based porous polymer-supported manganese heterogeneous catalysts
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A series of porphyrin-based porous polymers to support Mn heterogeneous catalysts (Mn/TFP-DPM, Mn/TFP-DPM-2, Mn/TFP-DPM-3, and Mn/TFP-DPM-4) in the selective oxidation of alcohols were designed. TFP-DPM and TFP-DPM-2 demonstrated micro/nanoscale spherical morphology, whereas TFP-DPM-3 and TFP-DPM-4 exhibited nanosheets structure. According to surface area and porosity analysis results, the specific surface areas of these catalysts were less than 300 m2 g–1. Thermogravimetric analysis indicated that the synthesized catalysts maintain their stability even at 300 °C. Catalysts Mn/TFP-DPM and Mn/TFP-DPM-3, which had the smallest and largest specific surface area among the four catalysts, respectively, were used to perform selective oxidation reaction of alcohols, with experimental results indicating that both have excellent catalytic performance. As these catalysts possess good catalytic performance despite their low specific surface area, we suggest that porphyrin-based porous polymer-supported Mn heterogeneous catalysts are promising materials for selective oxidation of alcohols.
- Chen, Jian,Zhang, Yan,Zhu, Dajian,Li, Tao
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- Superbenzene–Porphyrin Gas-Phase Architectures Derived from Intermolecular Dispersion Interactions
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A systematic series of superbenzene–porphyrin conjugates was synthesized and characterized. All conjugates show a high degree of cluster formation that correlates to the amount of tert-butylated hexa-peri-hexabenzocoronenes (tBuHBCs) attached to the porphyrin's periphery. Determined by mass spectrometry and X-ray diffraction, van der Waals (vdW) interactions like London dispersions (LD), stemming from solubilizing tert-butyl groups, were identified to be the major reason for the cluster formation. Cluster sizes comprised of more than twenty molecules with masses up to 70 000 Da were observed, which are rare examples of large architectures based on synthetic functional molecules, assembled by dispersion interactions. Novel strategies towards the design of solution processable functional materials, capable of dynamic transformations based on non-covalent synthesis can be envisioned.
- Lungerich, Dominik,Hitzenberger, Jakob F.,Hampel, Frank,Drewello, Thomas,Jux, Norbert
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- Structure-charge transport relationship of 5,15-dialkylated porphyrins
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5,15-Dialkyl-substituted porphyrins that are symmetrically capped with ethyl (C2-Por), butyl (C4-Por) and hexyl (C 6-Por) were synthesized and characterized. Molecular structure versus physical property relationship has been established through the analysis of planar charge transport using thin film transistor (TFT) structure.
- Zhou, Li,Xu, Zong-Xiang,Zhou, Ye,Feng, Yan,Zhou, Xiang-Ge,Xiang, Hai-Feng,Roy
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- The effect of porphyrins suspended with different electronegative moieties on the photovoltaic performance of monolithic porphyrin-sensitized solar cells with carbon counter electrodes
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Three D-π-A porphyrin sensitizers with different electronegative moieties (2,4,6-triphenyl-1,3,5-triazine, carbazole and triphenylamine) attached at the meso-position were designed and synthesized for monolithic dye-sensitized solar cells based on mesoscopic carbon counter electrodes. The effects of these different electronegative moieties on the photophysical, electrochemical and accordingly photovoltaic performance of the corresponding devices were investigated systematically. Electrochemical measurements indicate that the HOMO and LUMO energy levels could be tuned through the introduction of different electronegative groups onto the backbone of D-π-A porphyrin molecules. Current-voltage characteristics indicate that the Jsc and Voc of the DSSCs based on WH-C3, WH-C4 and WH-C5 increase as the electron-donating ability of their donors enhance in the order of WH-C3 sc) of 11.43 mA cm-2, an open circuit voltage (Voc) of 633.84 mV, and a fill factor (FF) of 0.69, corresponding to an overall conversion efficiency (η) of 5.00%.
- Chen, Jiangzhao,Ko, Songguk,Liu, Linfeng,Sheng, Yusong,Han, Hongwei,Li, Xiong
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- Remarkable isolation, structural characterisation and electrochemistry of unexpected scrambling analogues of 5-ferrocenyl-10,20-diphenylporphyrin
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Selective condensation of 5-ferrocenyldipyrromethane, 1, and dipyrromethane, 2, with benzaldehyde, 3, led to 5-ferrocenyl-10,20- diphenylporphyrin, 5. During the condensation, an unusually large amount of scrambling was observed which led to the isolation of two further ferrocenylated porphyrin analogues 6 and 7. The structure of 6 was confirmed by a single-crystal X-ray study. A mechanism is proposed for this atypical scrambling which is likely to involve acid-catalysed reversion of the dipyrromethane synthesis. 1H NMR further elucidated the structures of each complex and showed the existence of atropisomerism. An electrochemical study (cyclic voltammetry, Osteryoung square wave and linear sweep voltammetry) showed that there exists a linear relationship between the sum of the group electronegativities of meso substituents of the obtained porphyrins and the formal reduction potentials of the two observed ring-centred reduction processes, the meso substituent ferrocenyl-based oxidation process and the first ring-centred oxidation wave. These four relationships could be mathematically quantified. Due to the strong electron-withdrawing properties of the oxidised ferrocenium group, the second ring centred oxidation wave fell outside the potential window of dichloromethane as solvent. The Royal Society of Chemistry.
- Auger, Aurelien,Muller, Alfred J.,Swarts, Jannie C.
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- Synthesis and properties of meso-unsubstituted 3-pyrrolyl boron dipyrromethene
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We report the synthesis of meso-free 3-pyrrolyl boron dipyrrin (3-pyrrolyl BODIPY) and fully unsubstituted meso-free boron dipyrrin (parent BODIPY) in one pot under simple reaction conditions by treating meso-free dipyrromethane with pyrrole in CHCl3 followed by oxidation with DDQ, neutralization with triethylamine and complexation with BF3.OEt2. The compounds were separated by column chromatography on silica and isolated in 6-10 % yields. The compounds are characterized by HR-MS mass, NMR, absorption, electrochemical and fluorescence techniques. The meso-free 3-pyrrolyl BODIPY exhibit red shifted absorption and emission bands compared to meso-free BODIPY. The meso-free BODIPY exhibit green fluorescence and meso-free 3-pyrrolyl BODIPY exhibit orange fluorescence in solution. Furthermore, compared to meso-phenyl 3-pyrrolyl BODIPY, the meso-free 3-pyrrolyl BODIPY is more strongly fluorescent with nearly 41 % increase in quantum yield. Electrochemical studies showed that meso-free 3-pyrrolyl BODIPY exhibit one irreversible reduction and one ill-defined oxidation indicating that the compound is not stable under redox conditions. Computational studies revealed that meso-free pyrrolyl BODIPY has reduced HOMO-LUMO gap compared to parent meso-free BODIPY. Furthermore, the meso-free 3-pyrrolyl BODIPY exhibit much higher quantum yield compared to meso-aryl analogue of 3-pyrrolyl BODIPY. [Figure not available: see fulltext.]
- Lakshmi, Vellanki,Shaikh, Mushtaque S.,Ravikanth, Mangalampalli
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- Nonlinear optical properties of symmetrical and asymmetrical porphyrin derivatives with click chemistry modification
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The novel kind of charge-transfer porphyrin complexes with symmetrical and asymmetrical side groups were synthesized by the high-yielding [2?+?2] click chemistry reaction involved a two-step procedure. Both electrochemical and UV–vis studies were characterized and proved that the side groups of the porphyrin complexes played an important role on optical properties and energy gaps. The novel series did show the narrower band gap and broader absorption in the visible and near infrared region. As the side groups, the click moieties also affected the third-order nonlinear optical responses, and all the compounds exhibited the expected nonlinear optical properties which were affected by the chemical structures. The optical-limiting performance had also been studied, which was in agreement with the result of Z-scan experiments.
- Liu, Xiong,Wang, Dong,Gao, Hong,Yang, Zhou,Xing, Yan,Cao, Hui,He, Wanli,Wang, Huihui,Gu, Jianming,Hu, Huiying
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- A new approach way for white organic light-emitting diodes based on single emitting layer and large stokes shift
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New red dopant, DPPZ based on porphyrin moiety was synthesized. DPPZ showed UV-Vis and PL maximum values of 412 and 638 nm, indicating the large stokes shift. New blue host compound, TATa was also synthesized and used for co-mixed white emission. TATa exhibited UV-Vis. and PL maximum values of 403 nm and 463 nm in film state. Thus, when two compounds are used as co-mixed emitter in OLED device, there is no energy transfer from blue emission of TATa to DPPZ due to large stokes shift of DPPZ. Based on the PL result, it is available to realize two-colored white in PL and EL spectra. As a result of this, two-mixed compounds showed vivid their own PL emission peaks of 466 and 638 nm in film state. Also, white OLED device using two-mixed compounds system was fabricated. EL spectrum shows 481 and 646 nm peaks and two separate EL peaks. As the operation voltage is increased from 8 to 11 V, EL spectrum does not change the peak shape and maximum wavelength values. EL performance of white device showed 0.041 cd/A, 0.018 lm/W, and CIE (0.457, 0.331) at 8 V. Copyright
- Kim, Beomjin,Park, Youngil,Shin, Yunseop,Lee, Jiwon,Shin, Hwangyu,Park, Jongwook
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- Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening
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In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.
- Haldar, Ritesh,Batra, Kamal,Marschner, Stefan Michael,Kuc, Agnieszka B.,Zahn, Stefan,Fischer, Roland A.,Br?se, Stefan,Heine, Thomas,W?ll, Christof
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- Donor-acceptor copolymer based on dioctylporphyrin: Synthesis and application in organic field-effect transistors
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A novel alternating D-A copolymer, PPor-BT, with dioctylporphyrin (Por) as a donor unit and 5,6-bis(octyloxy)benzo-2,1,3-thiadiazole (BT) as an acceptor unit, was designed and synthesized by Pd-catalyzed Sonogashira-coupling reaction. The copolymer showed good solubility and film-forming ability. PPor-BT exhibited a broad absorption band from 350 to 950 nm with two peaks centered at 456 and 818 nm corresponding to the Soret band and Q-bands absorption of porphyrin segments, respectively. The employment of electron deficient BT unit to construct donor-acceptor structure observably broadened the absorption spectrum and enhanced the Q-band absorption of the porphyrin-based polymer. The HOMO and LUMO energy levels of the polymer are -5.06 eV and -3.63 eV, respectively. The solution-processed organic field-effect transistors (OFETs) were fabricated with bottom gate/top-contact geometry. The mobility of PPor-BT based OFEFs reached 4.3 × 10-5 cm2 V-1 s-1 with an on/off current ratio of 104. This mobility is among the highest values for porphyrin-based polymers.
- Wang, Xiaochen,Wen, Yugeng,Luo, Hao,Yu, Gui,Li, Xiaoyu,Liu, Yunqi,Wang, Haiqiao
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- The effect of pyridyl substituents on the thermodynamics of porphyrin binding to G-quadruplex DNA
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Most of the G-quadruplex interactive molecules reported to date contain extended aromatic flat ring systems and are believed to bind principally by π-π stacking on the end G-tetrads of the quadruplex structure. One such molecule, TMPyP4, (5,10,15,20-tetra(N-methyl-4-pyridyl)porphyrin), exhibits high affinity and some selectivity for G-quadruplex DNA over duplex DNA. Although not a realistic drug candidate, TMPyP4 is used in many nucleic acid research laboratories as a model ligand for the study of small molecule G-quadruplex interactions. Here we report on the synthesis and G-quadruplex interactions of four new cationic porphyrin ligands having only 1, 2, or 3 (N-methyl-4-pyridyl) substituents. The four new ligands are: P(5) (5-(N-methyl-4-pyridyl)porphyrin), P(5,10) (5,10-di(N-methyl-4-pyridyl)porphyrin), P(5,15) (5,15-di(N-methyl-4- pyridyl)porphyrin), and P(5,10,15) (5,10,15-tri(N-methyl-4-pyridyl)porphyrin). Even though these compounds have been previously synthesized, we report alternative synthetic routes that are more efficient and that result in higher yields. We have used ITC, CD, and ESI-MS to explore the effects of the number of N-methyl-4-pyridyl substituents and the substituent position on the porphyrin on the G-quadruplex binding energetics. The relative affinities for binding these ligands to the WT Bcl-2 promoter sequence G-quadruplex are: K TMPyP4 ≈ KP(5,15) > KP(5,10,15) >>> KP(5,10), KP(5). The saturation stoichiometry is 2:1 for both P(5,15) and P(5,10,15), while neither P(5) nor P(5,10) exhibit significant complex formation with the WT Bcl-2 promoter sequence G-quadruplex. Additionally, binding of P(5,15) appears to interact by an 'intercalation mode' while P(5,10,15) appears to interact by an 'end-stacking mode'.
- Rowland, Gerald B.,Barnett, Kerry,Dupont, Jesse I.,Akurathi, Gopalakrishna,Le, Vu H.,Lewis, Edwin A.
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- Ambient stable, hydrophobic, electrically conductive porphyrin hole-extracting materials for printable perovskite solar cells
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Fundamental properties of organic molecules such as symmetry and conjugation have a major impact on their functional properties and applications. In this study, we designed and synthesized hydrophobic, electrically conductive porphyrin derivatives using N-octyl phenothiazine as the donors and a porphyrin as the π-spacer in a D-π-D configuration. These materials are candidates for hole transport layers (HTL) within optoelectronic devices, and specifically perovskite solar cells (PSC). Detailed optical, electrical and electrochemical characterization of the porphyrin molecules were used to assess their properties, revealing good conductivity, clear electronic transitions and HOMO energy levels well aligned with the valence band of methylammonium lead iodide, the archetypal absorber in PSCs. We fabricated all-solution processed perovskite devices through screen-printing of the various layers and, adopting a carbon nanoparticle-graphene composite cathode, achieved a high photocurrent density of >19.5 mA cm-2 and power conversion efficiency of >11% for our porphyrin derivatives. In addition, by the introduction of hydrophobic octyl groups on the porphyrin substituents, we could achieve excellent water stability of our devices without the need for encapsulation, confirming the promise of these materials for stable HTLs. Such hydrophobic porphyrin systems will have broad academic and industrial interest for use in photovoltaics, light emitting diodes, photodetectors and other optoelectronic devices.
- Reddy, Govind,Katakam, Ramakrishna,Devulapally, Koteshwar,Jones, Lathe A.,Della Gaspera, Enrico,Upadhyaya, Hari M.,Islavath, Nanaji,Giribabu, Lingamallu
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- Synthesis of bisindolylmethane, bispyrrolylmethane, and indolylpyrrolylmethane derivatives via reductive heteroarylation
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An efficient and general reductive heteroarylation approach toward the synthesis of bisindolylmethane, bispyrrolylmethane, and indolylpyrrolylmethane derivatives has been developed. Thus, treatment of acylpyrrole or acylindole derivatives with indoles or pyrroles in the presence of a combination of sodium borohydride and acetic acid resulted in the formation of the title compounds in moderate to excellent isolated yields.
- Zhou, Hang,Huang, Zhuo,Huang, He,Song, Chuanjun,Chang, Junbiao
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- A New Potent Antimicrobial Metalloporphyrin
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A series of bis-acryl functionalized porphyrins and their corresponding metalloporphyrins (M=Co, Mn) were synthesized and investigated for their antimicrobial properties through MIC screening and bacteria time-kill kinetic studies. The Mn(III) 4-(bis)methylphenyl-substituted-porphyrins showed superior batericidal activities even in the dark with low hemotoxicity and good cytotoxicity profile.
- Jiang, Lu,Chee, Pei Lin,Gao, Jian,Gan, Ching Ruey Raymond,Owh, Cally,Lakshminarayanan, Rajamani,Jiang, Shan,Hor, T. S. Andy,Loh, Xian Jun
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p. 1007 - 1015
(2021/03/30)
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- Modular Synthesis of trans-A2B2-Porphyrins with Terminal Esters: Systematically Extending the Scope of Linear Linkers for Porphyrin-Based MOFs
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Differently functionalized porphyrin linkers represent the key compounds for the syntheses of new porphyrin-based metal–organic frameworks (MOFs), which have gathered great interest within the last two decades. Herein we report the synthesis of a large range of 5,15-bis(4-ethoxycarbonylphenyl)porphyrin derivatives, through Suzuki and Sonogashira cross-coupling reactions of an easily accessible corresponding meso-dibrominated trans-A2B2-porphyrin with commercially available boronic acids or terminal alkynes. The resulting porphyrins were fully characterized through NMR, MS, and IR spectroscopy and systematically investigated through UV/Vis absorption. Finally, selected structures were saponified to the corresponding carboxylic acids and subsequently proven to be suitable for the synthesis of surface-anchored MOF thin films.
- Marschner, Stefan M.,Haldar, Ritesh,Fuhr, Olaf,W?ll, Christof,Br?se, Stefan
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p. 1390 - 1401
(2020/12/14)
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- A Synthetic Strategy for Cofacial Porphyrin-Based Homo- and Heterobimetallic Complexes
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We present a straightforward and generally applicable synthesis route for cofacially linked homo- and heterobimetallic porphyrin complexes. The protocol allows the synthesis of unsymmetrical aryl-based meso-meso as well as β-meso-linked porphyrins. Our method significantly increases the overall yield for the published compound known as o-phenylene-bisporphyrin (OBBP) by a factor of 6.8. Besides the synthesis of 16 novel homobimetallic complexes containing MnIII, FeIII, NiII, CuII, ZnII, and PdII, we achieved the first single-crystal X-ray structure of an unsymmetrical cofacial benzene-linked porphyrin dimer containing both planar-chiral enantiomers of a NiII2 complex. Additionally, this new methodology allows access to heterobimetallic complexes such as the FeIII-NiII containing carbon monoxide dehydrogenase active site analogue. The isolated species were investigated by various techniques, including ion mobility spectrometry, DFT calculations, and UV/Vis spectroscopy. This allowed us to probe the influence of interplane distance on Soret band splitting.
- Schissler, Christoph,Schneider, Erik K.,Felker, Benjamin,Weis, Patrick,Nieger, Martin,Kappes, Manfred M.,Br?se, Stefan
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supporting information
p. 3047 - 3054
(2021/01/20)
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- C2 symmetric borneol-porphyrin hybrids: Synthesis, characterization, electronic structure and their anti-cancer behaviors
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A series of five C2 Symmetric A2B2 type borneol-porphyrin hybrids have been synthesized and characterized. Moreover, a detailed analysis of their optical and redox properties was carried out by comparing the results obtained via optical spectroscopy and electrochemistry. The current results demonstrated that the meso borneol-substitutions excitation coupled strongly with porphyrin core that leads to significant CD signals in the Soret band region, and molecular anti-cancer behaviors were also investigated.
- Dong, Xinyi,Fang, Xianying,Fu, Bo,Liang, Xu,Xu, Haijun,Yu, Xiaoxiao,Zhang, Zhen,Zhu, Weihua
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- Ligand-Directed Conformational Control over Porphyrinic Zirconium Metal-Organic Frameworks for Size-Selective Catalysis
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Zirconium-based metal-organic frameworks (Zr-MOFs) have aroused enormous interest owing to their superior stability, flexible structures, and intriguing functions. Precise control over their crystalline structures, including topological structures, porosity, composition, and conformation, constitutes an important challenge to realize the tailor-made functionalization. In this work, we developed a new Zr-MOF (PCN-625) with a csq topological net, which is similar to that of the well-known PCN-222 and NU-1000. However, the significant difference lies in the conformation of porphyrin rings, which are vertical to the pore surfaces rather than in parallel. The resulting PCN-625 exhibits two types of one-dimensional channels with concrete diameters of 2.03 and 0.43 nm. Furthermore, the vertical porphyrins together with shrunken pore sizes could limit the accessibility of substrates to active centers in the framework. On the basis of the structural characteristics, PCN-625(Fe) can be utilized as an efficient heterogeneous catalyst for the size-selective [4 + 2] hetero-Diels-Alder cycloaddition reaction. Due to its high chemical stability, this catalyst can be repeatedly used over six times. This work demonstrates that Zr-MOFs can serve as tailor-made scaffolds with enhanced flexibility for target-oriented functions.
- Yang, Liting,Cai, Peiyu,Zhang, Liangliang,Xu, Xiaoyi,Yakovenko, Andrey A.,Wang, Qi,Pang, Jiandong,Yuan, Shuai,Zou, Xiaodong,Huang, Ning,Huang, Zhehao,Zhou, Hong-Cai
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supporting information
p. 12129 - 12137
(2021/08/23)
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- Modifiable hyperconjugation triple molten porphyrin dimer strong two-photon absorption material and preparation thereof
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The invention relates to a modifiable hyperconjugation triple molten porphyrin dimer strong two-photon absorption material and preparation thereof. In two edge meso positions of a porphyrin dimer, oneof the two edge meso positions of the porphyrin dimer is provided with anilino, and the other of the two edge meso positions of the porphyrin dimer is provided with acetanilino. Compared with the prior art, the preparation method comprises the following steps: selectively modifying aniline groups on single porphyrin with vacancy at double meso sites in a unilateral manner, performing protection in advance, further separating out a symmetrical molten porphyrin dimer with two acetanilide groups through low-temperature oxidation and low-temperature extraction modes, and finally preparing a target compound with one anilino group and one acetanilino group through a unilateral deprotection reaction, namely the asymmetric triple molten porphyrin dimer TFP. The material not only has the strong TPA characteristic of the triple molten porphyrin dimer, but also is very easy to modify, provides possibility for preparing diversified nonlinear and other functional materials with a wider applicationrange, and has a good application prospect.
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Paragraph 0045; 0049
(2020/11/09)
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- Triple molten porphyrin dimer covalent functionalized single-walled carbon nanotube nonlinear nano hybrid material and preparation method thereof
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The invention relates to a triple molten porphyrin dimer covalent functionalized single-walled carbon nanotube non-linear nano hybrid material and a preparation method thereof. The non-linear nano hybrid material is formed by connecting a triple molten porphyrin dimer TFP to the surface of SWCNT through covalent bonds. Compared with the prior art, the organic-inorganic covalent functionalized nanofunctional material is prepared by connecting TFP to the surface of SWCNT through covalent bonds and the azo salt free radical addition reaction instead of simply and physically mixing the two different optical functional materials, and compared with a traditional material, the prepared material not only has enhanced nonlinear optical properties in the nanosecond visible light field, but also canconvert saturated absorption of a traditional material into anti-saturated absorption in the femtosecond near-infrared field, and has a very wide application prospect.
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(2020/12/30)
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- Double Porphyrin Cage Compounds
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The synthesis and characterization of double porphyrin cage compounds are described. They consist of two porphyrins that are each attached to a diphenylglycoluril-based clip molecule via four ethyleneoxy spacers, and are linked together by a single alkyl chain using “click”-chemistry. Following a newly developed multistep synthesis procedure we report three of these double porphyrin cages, linked by spacers of different lengths, i.e. 3, 5, and 11 carbon atoms. The structures of the double porphyrin cages were fully characterized by NMR, which revealed that they consist of mixtures of two diastereoisomers. Their zinc derivatives are capable of forming sandwich-like complexes with the ditopic ligand 1,4-diazabicyclo[2,2,2]octane (dabco).
- Elemans, Johannes A. A. W.,Klop, Jo?lle-Rose,Mabesoone, Mathijs F. J.,Meijer, Eline M.,Nolte, Roeland J. M.,Peters, Theo P. J.,Rowan, Alan E.,Stout, Kathleen,Visschers, Fabian L. L.,White, Paul B.,van den Berg, Jeroen
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p. 7087 - 7100
(2020/12/07)
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- Accepting to Donate: NDI-Based Small Molecule as a Donor for Bulk Heterojunction Binary Solar Cells
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A small molecular D-π-A-π-D triad NDIP consisting of naphthalenediimide (NDI) as an acceptor and porphyrin as a donor was synthesized. NDIP exhibits an intense absorption from visible to NIR region (400 nm to 1000 nm) with high molecular extinction coefficient. Endowed with excellent absorption and good charge carrier mobility, the molecule was used as a donor, against the normal perception as an acceptor due to the electron-deficient nature of NDI, in the binary bulk heterojunction solar cells with PCBM as an acceptor. The cell demonstrated remarkable power conversion efficiency of 8.45 % with extremely low Eloss of 0.40 eV, which is also the best recorded for NDI based small molecule organic solar cells.
- Mishra, Ruchika,Sujesh,Archana,Kaushik, Ayushi,Gupta, Gaurav,Singhal, Rahul,Sharma, Ganesh D.,Sankar, Jeyaraman
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supporting information
p. 1603 - 1610
(2020/01/22)
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- A dinuclear porphyrin-macrocycle as efficient catalyst for the hydrogen evolution reaction
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We report an unprecedented dinuclear catalyst for the electrochemical hydrogen evolution reaction (HER). A macrocyclic porphyrin complex comprising two nickel centres connected via redox mediating linker molecules gives rise to efficient catalysis, significantly outperforming a mononuclear reference catalyst. This journal is
- J?kel, Julia,Schwer, Fabian,Von Delius, Max,Apfel, Ulf-Peter
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supporting information
p. 14179 - 14182
(2020/11/24)
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- Bis-Anthracene Fused Porphyrin as an Efficient Photocatalyst: Facile Synthesis and Visible-Light-Driven Oxidative Coupling of Amines
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Development of high-performance photocatalysts for the conversion of amines is of great importance, but has remained a challenging task. Here, a bis-anthracene fused porphyrin (AFP) was synthesized in a high yield by a facile synthetic protocol, which involves a Suzuki coupling for the conjugation of two anthracene groups with a porphyrin ring, followed by oxidative cyclodehydrogenation. When serving as a photocatalyst, AFP exhibits an outstanding photocatalytic performance for the visible-light-induced aerobic oxidation of amines to imines at ambient conditions. Density functional theory calculations revealed that the low energy band gap, caused by the large planar and π-extended porphyrin structure of AFP, contributed to its high photocatalytic performance.
- Droste, J?rn,Hansen, Michael Ryan,Klabunde, Sina,Mai, Yiyong,Yin, Yucheng,Yu, Chunyang,Zhang, Pengfei
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supporting information
p. 16497 - 16503
(2020/12/01)
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- Synthesis and characterization of novel 5-monocarbohydrate-10,20- bis -aryl-porphyrins
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The synthesis of derivatives bearing glucose or galactose units linked by an acrylate spacer to one free meso position of a bis-aryl-porphyrin macrocycle was developed and characterized by standard spectroscopic techniques. The new mono-substituted gluco- and galacto-porphyrin derivatives 5-8 present an alternative to the widespread tetra-aryl porphyrin functionalization. Singlet oxygen studies showed a comparable singlet oxygen production with TPP. Furthermore, the less bulky architectures here synthesized present an opportunity to enhance the PDT and PDI capabilities of glycoporphyrins with a simple synthetic modification at one of the meso positions.
- Figueira, Flávio,Louren?o, Leandro M. O.,Neves, Maria G. P. M. S.,Cavaleiro, José A. S.,Tomé, Jo?o P. C.
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p. 330 - 339
(2019/09/17)
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- Short-Chained Anthracene Strapped Porphyrins and their Endoperoxides
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The syntheses of short-chained anthracene-strapped porphyrins and their Zn(II)complexes are reported. The key synthetic step is a [2+2] condensation between a dipyrromethane and an anthracene bisaldehyde, 2,2'-((anthracene-9,10-diylbis(methylene))bis(oxy))dibenzaldehyde. Following exposure to white light, self-sensitized singlet oxygen and the anthracene moieties underwent [4+2] cycloaddition reactions to yield the corresponding endoperoxides. 1H NMR studies demonstrate that the endoperoxide readily formed in [D]chloroform and decayed at 85 °C. X-ray crystallography and absorption spectroscopy were used to confirm macrocyclic distortion in the parent strapped porphyrins and endoperoxides. Additionally, X-ray crystallography indicated that endoperoxide formation occurred exclusively on the outside face of the anthracene moiety.
- Callaghan, Susan,Flanagan, Keith J.,O'Brien, John E.,Senge, Mathias O.
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- Synthesis and photodynamic activity of novel non-symmetrical diaryl porphyrins against cancer cell lines
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Photodynamic therapy (PDT)of cancer uses photosensitizers (PS), a light source and oxygen to generate high levels of reactive oxygen species (ROS), that exert a cytotoxic action on tumor cells. Recently, it has been shown that mixed non-symmetrical diaryl porphyrins, with two different pendants, are more photodynamically active than symmetrical diaryl porphyrins. In the present study, we investigate the in vitro photodynamic effects of four novel non-symmetrical diaryl porphyrins, two of which bear one pentafluoro-phenyl and one bromo-alkyl (apolar)pendant, whereas the two others bear one pentafluoro-phenyl and one cationic pyridine pendant. The four compounds were tested in a small panel of human cancer cell lines, and their photodynamic activities were compared with that of m-THPC (Foscan), currently the most successful PS approved for clinical use in cancer PDT. The results of the cytotoxicity studies indicate that the two molecules bearing the cationic pendant are more potent in vitro than those with the apolar pendant, and that they are as potent as Foscan. To gain further insights into the mechanism of PS-induced phototoxicity, induction of apoptotic, autophagic and necrotic cell death, and generation of reactive oxygen species (ROS)were evaluated in cancer cells following exposure to the PSs and irradiation. The effect of the PSs on the migratory activity of the cells was also assessed. The data obtained from this work support a greater potency of diaryl porphyrins with a positive charge in inducing cell death, as compared to those with the bromo-alkyl pendant; most importantly, some of these novel compounds exhibit features that might make them superior to the clinically approved PS Foscan.
- Caruso, Enrico,Cerbara, Monica,Malacarne, Miryam Chiara,Marras, Emanuela,Monti, Elena,Gariboldi, Marzia Bruna
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- METHOD FOR PREPARING PORPHYRIN DERIVATE
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The present invention relates to a method for manufacturing porphyrin derivatives, comprising a step of oxidizing porphyrinogen by oxygen bubbling under a metal catalyst to synthesize porphyrin derivatives. Therefore, since the method for manufacturing porphyrin derivatives of the present introduced a method of oxidization using oxygen bubbling under the metal catalyst without using a quinone-based oxidizing agent, it is possible to increase the yield of porphyrin derivatives and have an effect that a refining process is very easy.COPYRIGHT KIPO 2019
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Paragraph 0070-0073
(2019/05/22)
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- Synthesis of dipyrrolo-diazepine derivatives via intramolecular alkyne cyclization
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A regioselective approach was developed for the synthesis of dipyrrolo-diazepine derivatives. The synthetic route to dipyrrolo-diazepines first involves the synthesis of dipyrromethanes, followed by reaction of propargyl bromide in the presence of NaH to attach one alkyne functionality to the pyrrole nitrogen atom. Intramolecular heterocyclization with NaH in DMF between the alkyne functionality and pyrrole nitrogen atom gave the desired structures in good yields.
- Bask?n, D?lge?,?etinkaya, Yasin,Balci, Metin
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p. 4062 - 4070
(2018/06/14)
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- Cross-linked cyclic porphyrin derivative and method for preparing the same
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The present invention relates to a cross-linked cyclic porphyrin derivative and to a manufacturing method thereof. By using the crosslinked cyclic porphyrin derivative, it is possible to measure a change in color selectively when cations and anions are present together, and thus the cations and the anions, preferably Li cations and halogen anions, can be selectively detected without any separate labels.COPYRIGHT KIPO 2018
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Paragraph 0105-0110
(2018/07/07)
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- C-Bridged Bispyrrolidines and Bispiperidines as New Ligands
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The preparation of methylene-bridged C2-symmetric nitrogen-heterocycles as a new class of ligands is described, including methylene-bridged pyridines, quinolones, piperidines and pyrrolidines. These methylene-bridged aromatic systems are obtained via a microwave assisted Ziegler-type reaction. The separation of diastereomers and the application of the copper complexes of these ligands for cyclopropanation reactions proves the applicability of these new types of ligands.
- Stumpf, Tim-Daniel J.,Steinbach, Manfred,H?ltke, Magdalene,Heuger, Gerold,Grasemann, Franka,Fr?hlich, Roland,Schindler, Siegfried,G?ttlich, Richard
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p. 5538 - 5547
(2018/10/25)
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- Deciphering the potentiometric properties of (porphinato)zinc(ii)-derived supramolecular polymers and related superstructures
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Because modulating the structure-function relationships of π-conjugated superstructures opens fresh opportunities to tune the electronic structures of semiconducting materials, self-assembled architectures have emerged as pivotal candidates to engineer optoelectronic devices. While the photophysical and electrical properties of 1-dimensional supramolecular polymers have been extensively explored, establishing their fundamental potentiometric properties using reliable electrochemical measurements has been less scrutinized and would benefit the engineering of semiconducting materials. In this regard, elucidating the energy level of valence and conduction bands that delineate the electronic structure of self-assemblies is critical to unveiling the parameters that regulate their structure-function properties. In the present contribution, design principles to engineer 2-dimensional nanosheets, nanowires, fibers and amorphous solids from (porphinato)zinc(ii) (PZn) building blocks have been elucidated by modifying the structural properties of the side chains that flank PZn-based cores. As these self-assemblies feature identical redox-active building blocks but evidence different solid-state morphologies, the elucidation of their potentiometric properties reveals important structural parameters that regulate the potentials at which holes and electrons are injected into the valence and conduction bands of these hierarchical materials. While self-assembly conformations modestly impact valence band energies, superstructures built from H-type aggregates feature a conduction band energy stabilized by more than 350 meV with respect to those constructed from J-type aggregates.
- Liu, Chuan,Liu, Kaixuan,Klutke, Jared,Ashcraft, Adam,Steefel, Samantha,Olivier, Jean-Hubert
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supporting information
p. 11980 - 11991
(2018/11/26)
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- Singlet-singlet energy transfer in carbazole-porphyrin dyads and triads
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Donor-π-Acceptor (D-π-A) type carbazole-porphyrin dyads and triads were synthesized in good yields through palladium catalyzed coupling reactions. The length of the spacer between the D (carbazole) and A (porphyrin) was varied from “phenylethyne” to “ethyne linkage”. The effect of the linker length on the spectral properties of these D-π-A dyads and triads was studied. The N-butyl-3-ethynyl-carbazole was coupled with different porphyrins bearing either one or two meso-p-iodophenyl group/meso-bromo groups using palladium catalyst. All the dyads and triads were characterized by MALDI-MS, NMR, UV–vis absorption, fluorescence and cyclic voltammetry techniques. The S1 emission dynamics were analyzed by time-resolved spectroscopy (TCSPC); an efficient energy transfer up to 84% was observed from donor groups to the porphyrin core. Electrochemical studies revealed that, compounds having freebase porphyrin components are difficult to reduce as indicated by the cathodic shift in their reduction potentials. On the contrary, the compounds having zinc porphyrin components are easy to reduce as reflected by the anodic shift in their reduction potentials. The lowest HOMO-LUMO gap was found for the dyad which has short linker between D and A.
- Balsukuri, Naresh,Gupta, Iti
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p. 223 - 233
(2017/05/29)
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- Porphyrin based push-pull conjugates as donors for solution-processed bulk heterojunction solar cells: A case of metal-dependent power conversion efficiency
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Solution-processed bulk-heterojunction organic solar cells have been achieved using unsymmetrical metalloporphyrin-PBI dyads as small molecular donors. Due to panchromatic absorption, a photon-to-current conversion efficiency of 6.18% was obtained for 3-Zn:PC71BM with a remarkable energy loss (Eloss) of 0.60 eV, which is in line with the best values recorded so far for porphyrin-based small-molecular donors.
- Mishra, Ruchika,Regar, Ramprasad,Singhal, Rahul,Panini, Piyush,Sharma, Ganesh D.,Sankar, Jeyaraman
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supporting information
p. 15529 - 15533
(2017/08/09)
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- Synthesis of dipyrromethanes in aqueous media using boric acid
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Boric acid acts as an efficient and green catalyst for the condensation reaction of pyrrole and aldehydes in aqueous medium to produce parallel library of dipyrromethanes including new compound analogue, meso-acetyldipyrromethane in moderate to good yield. The use of boric acid as catalyst and selective reactivity of aldehydes over ketones in its presence, and water as reaction medium are important attributes in the present protocol.
- Singhal, Anchal,Singh, Snigdha,Chauhan, Shive M. S.
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p. 144 - 151
(2018/05/09)
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- NANOPARTICLES FOR PHOTODYNAMIC THERAPY, X-RAY INDUCED PHOTODYNAMIC THERAPY, RADIOTHERAPY, CHEMOTHERAPY, IMMUNOTHERAPY, AND ANY COMBINATION THEREOF
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Metal-organic frameworks (MOFs) comprising photosensitizers are described. The MOFs can also include moieties capable of absorbing X- rays and/or scintillation. Optionally, the photosensitizer or a derivative thereof can form a bridging ligand of the MOF. Further optionally, the MOF can comprise inorganic nanoparticles in the cavities or channels of the MOF or can be used in combination with an inorganic nanoparticle. Also described are methods of using MOFs and/or inorganic nanoparticles in photodynamic therapy or in X-ray induced photodynamic therapy, either with or without the co-administration of one or more immunotherapeutic agent and/or one or more chemotherapeutic agent.
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Page/Page column 61
(2016/05/24)
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- Synthesis, photophysical, electrochemical and electrochemiluminescence properties of A2B2 zinc porphyrins: The effect of π-extended conjugation
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The synthesis of two A2B2 porphyrins, {5,15-bis-[4-(octyloxy)phenyl]-porphyrinato}zinc(ii) (4) and {5,15-bis-(carbazol-3-yl-ethynyl)-10,20-bis-[4-(octyloxy)phenyl]-porphinato}-zinc(ii) (9), is reported. Their photophysical properties were studied by steady-state absorption and emission. Substituting the carbazolylethynyl moieties at two of the meso positions results in a large bathochromic shift of all the absorption bands, a notable increase in the absorption coefficient of the Q(0,0) band, and higher fluorescence quantum yield compared to porphyrin 4, with two unsubstituted meso positions. Cyclic voltammetry and digital simulation show that electrogenerated radical ions of 9 are more stable than those of 4. The lack of substituents at the meso positions of 4 leads to dimerization reactions of the radical cation. Despite this, the annihilation reaction of 4 and 9 produces very similar electrogenerated chemiluminescence (ECL) intensity. Spectroelectrochemical experiments demonstrate that the electroreduction of 9 leads to a strong absorption band that might quench the ECL.
- Galván-Miranda, Elizabeth K.,Castro-Cruz, Hiram M.,Arturo Arias-Orea,Iurlo, Matteo,Valenti, Giovanni,Marcaccio, Massimo,Macías-Ruvalcaba, Norma A.
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p. 15025 - 15038
(2016/07/06)
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- Exploring the Strength of the H-Bond in Synthetic Models for Heme Proteins: The Importance of the N?H Acidity of the Distal Base
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The distal hydrogen bond (H-bond) in dioxygen-binding proteins is crucial for the discrimination of O2with respect to CO or NO. We report the preparation and characterization of a series of ZnIIporphyrins, with one of three meso-phenyl rings bearing both an alkyl-tethered proximal imidazole ligand and a heterocyclic distal H-bond donor connected by a rigid acetylene spacer. Previously, we had validated the corresponding CoIIcomplexes as synthetic model systems for dioxygen-binding heme proteins and demonstrated the structural requirements for proper distal H-bonding to CoII-bound dioxygen. Here, we systematically vary the H-bond donor ability of the distal heterocycles, as predicted based on pKavalues. The H-bond in the dioxygen adducts of the CoIIporphyrins was directly measured by Q-band Davies-ENDOR spectroscopy. It was shown that the strength of the hyperfine coupling between the dioxygen radical and the distal H-atom increases with enhanced acidity of the H-bond donor.
- Alberti, Mariza N.,Polyhach, Yevhen,Tzirakis, Manolis D.,T?dtli, Laura,Jeschke, Gunnar,Diederich, Fran?ois
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supporting information
p. 10194 - 10202
(2016/07/19)
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- Solvent-dependent moulding of porphyrin-based nanostructures: solid state, solution and on surface self-assembly
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A novel porphyrin derivative 1?Zn was synthesised in order to mimic the self-assembly properties of natural light-harvesting antennas and its self-assembly behaviour in solution and in solid state were studied by NMR and X-Ray spectroscopies. The self-assembly of this molecule was triggered in apolar solvents and studied in solution by UV-Vis spectroscopy, suggesting it is able to form slipped face-to-face aggregates, or J-aggregates. The nanoscopic and microscopic morphology of the aggregates was elucidated by atomic force microscopy, revealing the formation of extended two-dimensional structures.
- Dor?evi?, Luka,Demitri, Nicola,Bonifazi, Davide
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p. 753 - 761
(2016/10/20)
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- Porphyrin compound and preparation method and application thereof in surface enhanced Raman probe
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The invention relates to a porphyrin compound and a preparation method and an application thereof in a surface enhanced Raman probe. The porphyrin compound is 5-[4-(N,N-dimethylamino formyl)phenyl]-15-(4-carboxyl phenyl)porphyrin, and has the structure represented by the formula (I). One end of the prepared porphyrin compound is a carboxyl group which can be firmly adsorbed on the surface of titanium dioxide, and the other end of the prepared porphyrin compound is thiol ester which is adsorbed on a silver surface to form an S-Ag bond. Titanium dioxide nanoparticles and silver nanoparticles form a stable and ordered composite material under connective action of the molecule, and a stable and ordered SERS substrate is formed. The mark molecule is not only a template agent for the substrate but also has a stable signal on the substrate, and has a broad application prospect.
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-
Paragraph 0028; 0029; 0030; 0032
(2017/01/17)
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- Synthesis and self-assembly of DNA-chromophore hybrid amphiphiles
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DNA based spherical nanostructures are one of the promising nanostructures for several biomedical and biotechnological applications due to their excellent biocompatibility and DNA-directed surface addressability. Herein, we report the synthesis and amphiphilicity-driven self-assembly of two classes of DNA (hydrophilic)-chromophore (hydrophobic) hybrid amphiphiles into spherical nanostructures. A solid-phase "click" chemistry based modular approach is demonstrated for the synthesis of DNA-chromophore amphiphiles. Various spectroscopic and microscopic analyses reveal the self-assembly of the amphiphiles into vesicular and micellar assemblies with the corona made of hydrophilic DNA and the hydrophobic chromophoric unit as the core of the spherical nanostructures.
- Albert, Shine K.,Golla, Murali,Thelu, Hari Veera Prasad,Krishnan, Nithiyanandan,Deepak, Perapaka,Varghese, Reji
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supporting information
p. 6960 - 6969
(2016/07/30)
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- Mild microwave-assisted synthesis of dipyrromethanes and their analogues
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The Mannich reaction between pyrroles or indoles and Eschenmoser's salt (dimethylmethylideneammonium iodide) forms N,N-dimethylamino-methylated derivatives in good to excellent yields. The reaction is highly regioselective, and for pyrroles both 2-and 3-s
- Xiong, Ruisheng,Borbas, K. Eszter
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p. 484 - 488
(2015/04/14)
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- Dye for dye-sensitized solar cells and dye-sensitized solar cells using the same
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The present invention refers to dye-sensitized solar cell for methylcarbapenem derivative having hetero cyclic thiol derivative synthesis and relates to dye-sensitized solar cell to using the computer protocol [formula 1] is a dye which represented by which may model, synthetic dye and designing a dye that is a similar current-voltage characteristics to 100,000.. In particular, said is a dye which represented by [formula 1] a large hyperpolarizability price and excellent condensation ability degree of efficiency and, exhibits high dipole moment. [Formula 1] (by machine translation)
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Paragraph 0096-0100
(2017/01/02)
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- Enantiotopos-selective C-H oxygenation catalyzed by a supramolecular ruthenium complex
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Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol%). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive C-H bond and suggest-in line with the kinetic isotope effect-an oxygen rebound mechanism for the reaction.
- Frost, James R.,Huber, Stefan M.,Breitenlechner, Stefan,Bannwarth, Christoph,Bach, Thorsten
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supporting information
p. 691 - 695
(2015/03/04)
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- An efficient synthesis of porphyrins with different meso substituents that avoids scrambling in aqueous media
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We have developed new conditions that afford regioisomerically pure trans-A2B2-, A3B-, and trans-AB2C-porphyrins bearing aryl and arylethynyl substituents. The porphyrins were prepared by the acid-catalyzed condensation of dipyrromethanes with aldehydes followed by oxidation with p-chloranil or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Optimal conditions for the condensation were identified after examining various reaction parameters such as solvent composition, acid concentration, and reaction time. The conditions identified (for aromatic aldehydes: EtOH/H2O 4:1, [DPM] = 4 mM, [aldehyde] = 4 mM, [HCl] = 38 mM, 16 h; for arylethynyl aldehydes: THF/H2O 2:1, [DPM] = 13 mM, [aldehyde] = 13 mM, [HCl] = 150 mM, 3 h) resulted in the formation of porphyrins in yields of 9-38% without detectable scrambling. This synthesis is compatible with diverse functionalities such as ester or nitrile. In total, 20 new trans-A2B2-, A3B-, and trans-AB2C-porphyrins were prepared. The scope and limitations of the two sets of reaction conditions have been explored. The methodological advantage of this approach is its straightforward access to building blocks and the formation of the porphyrin core in higher yields than by any other methodology and by using environmentally benign and nonhazardous chemicals.
- Nowak-Krl, Agnieszka,Plamont, Rmi,Canard, Gabriel,Edzang, Judicaelle Andeme,Gryko, Daniel T.,Balaban, Teodorsilviu
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supporting information
p. 1488 - 1498
(2015/01/30)
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- Molecular engineering of boryl oxasmaragdyrins through peripheral modification: Structure-efficiency relationship
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Expanded porphyrins with the absorption profile down to the infrared region through increased p-conjugation are suitable candidates for a low energy sensitizer. Oxasmaragdyrin boron complexes, a class of aromatic-coremodified expanded porphyrin with 22 π -electrons, have been recently utilized as an efficient low energy sensitizer in dye-sensitized solar cells. In this paper, we have prepared a series of eight novel boryl oxasmaragdyrins through molecular engineering on the periphery and their overall photovoltaic performances in dye-sensitized solar cells are evaluated. With the help of photophysical, electrochemical, and photovoltaic studies, it is revealed that molecular structure, especially the number and position of the donor-acceptor groups play a pivotal role in their photovoltaic performance. Presence of the two well-separated split Soret bands in the 400-500 nm region of UV/Vis spectrum ensures broader coverage of absorption wavelengths. Even though the two-an-choring-group dyes (SM5-SM8 ) bind strongly to TiO2 compared to one-anchoring-group dyes (SM1-SM4), the latter have superior photovoltaic performance than the former. Dye SM1 , with two hexyloxyphenyl donors and one carboxylic acid anchor showed the best overall conversion efficiency of 4.36% (JSC = 10.91 mAcm-2 ; VOC = 0.59 V; FF = 0.68). This effective modulation of photovoltaic performance through structural engineering of the dyes will serve as a guideline for the future design of efficient low energy light-harvesting sensitizers.
- Mane, Sandeep B.,Hung, Chen-Hsiung
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p. 4825 - 4841
(2015/03/18)
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- The effect of different alkyl chains on the photovoltaic performance of D-π-A porphyrin-sensitized solar cells
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In this study, a series of novel D-π-A porphyrin sensitizers with different alkyl chains were designed and synthesized for dye-sensitized solar cells. The effects of different alkyl chains (methyl, methoxyl and hexyloxy groups) on the photophysical, electrochemical and photovoltaic performance were investigated systematically. The results indicate that the molar extinction coefficients of three dyes normally increase as the alkyl chain length increases. Furthermore, it is also found that the incident photo-to-current conversion efficiencies (IPCEs), short circuit current (Jsc) and open circuit voltage (Voc) of the dye-sensitized solar cells (DSSCs) based on WH-C1, YD20 and WH-C2 increase with the elongation of alkyl chains in the order of WH-C1 sc of 13.10 mA cm-2, a Voc of 831.10 mV, and a fill factor (FF) of 0.70.
- Chen, Jiangzhao,Ko, Songguk,Liu, Linfeng,Sheng, Yusong,Han, Hongwei,Li, Xiong
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p. 3736 - 3746
(2015/05/20)
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- Nanoscale metal-organic framework for highly effective photodynamic therapy of resistant head and neck cancer
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Photodynamic therapy (PDT) is an effective anticancer procedure that relies on tumor localization of a photosensitizer followed by light activation to generate cytotoxic reactive oxygen species (e.g., 1O2). Here we report the rational design of a Hf-porphyrin nanoscale metal-organic framework, DBP-UiO, as an exceptionally effective photosensitizer for PDT of resistant head and neck cancer. DBP-UiO efficiently generates 1O2 owing to site isolation of porphyrin ligands, enhanced intersystem crossing by heavy Hf centers, and facile 1O2 diffusion through porous DBP-UiO nanoplates. Consequently, DBP-UiO displayed greatly enhanced PDT efficacy both in vitro and in vivo, leading to complete tumor eradication in half of the mice receiving a single DBP-UiO dose and a single light exposure. NMOFs thus represent a new class of highly potent PDT agents and hold great promise in treating resistant cancers in the clinic.
- Lu, Kuangda,He, Chunbai,Lin, Wenbin
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supporting information
p. 16712 - 16715
(2015/02/19)
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- Alternating copolymerization of CO2 and propylene oxide catalyzed by C2v-porphyrin cobalt: Selectivity control and a kinetic study
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Some C2v (Cs)-porphyrin cobalt complexes have been devised, synthesized and utilized as efficient catalysts in combination with dimethylaminopyridine for the alternating copolymerization of propylene oxide and carbon dioxide. The C2v-catalyst [5,15-diphenylporphyrin]cobalt(III) chloride (1d) has demonstrated excellent reactivity and selectivity under optimized conditions. The axial counterions and the substituents of these metalloporphyrins exhibited distinct infection on the catalytic activity and selectivity. Synchronously, preliminary kinetic investigations of this reaction were achieved by using two catalyst systems illustrating the activation energies of copolymerization and coupling reaction, respectively. A competition mechanism between the polymerization and cycloaddition of propylene oxide and CO2 has been carefully proposed according to our experimental results.
- Jiang, Xu,Gou, Faliang,Jing, Huanwang
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p. 159 - 167
(2014/05/06)
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- Design and synthesis of perpendicularly connected metal porphyrin-imide dyads for two-terminal wired single molecular diodes
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Four different porphyrin-imide dyads bearing different central metals (zinc or rhodium) and different substituents on the porphyrin macrocycles (tert-butyl or methoxy) were synthesized for single molecular diode measurements. The molecules were designed to separate the donor component (porphyrin) from the acceptor component (imide) by bonding in a perpendicular arrangement, thus enhancing the rectification properties. UV/Vis absorption spectra and density functional theory calculations showed that the design was successful and that the molecular orbitals of the dyads were the summation of the two components, with minimal interaction between them. The effect of the central metal was found to be significant, with the lowest energy absorption for the zinc dyads being attributed to the mixed state of charge transfer from porphyrin to imide and the Q band, whereas that of the rhodium dyads indicated insignificant charge-transfer character. Molecular diodes: Four types of donor-acceptor molecules based on perpendicularly connected porphyrin and naphthalenediimide having different central metals, zinc(II) and rhodium(III), have been designed and synthesized to create donor-acceptor systems with the desired functionalities for single molecular diodes (see figure). The effects of central metals on molecular orbitals provide strong indications that the Rh porphyrin-imide dyads will show different electronic properties to the Zn molecules.
- Handayani, Murni,Gohda, Syun,Tanaka, Daisuke,Ogawa, Takuji
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p. 7655 - 7664
(2014/07/07)
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- Synthesis of trans-A2B2- and trans-A2BC-porphyrins with polar 4′-(dimethylamino)tolan-4-yl substituents, and a screening protocol for vapor-phase deposition on metal surfaces
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The role of polar 4-[p-(dimethylamino)phenylethynyl]phenyl substituents, with a calculated dipole moment of 3.35 Debye, in the self-assembly of trans-A2B2- and A2BC-substituted porphyrins was explored in the solid state by X-ray crystallography, and on an Au(111) surface by scanning tunneling microscopy (STM). Our results demonstrate that the dipolar character of these substituents blocks the 2D self-assembly of porphyrins into larger ordered domains on Au(111) at low coverage, whereas antiparallel dipole - dipole interactions govern the molecular ordering in the crystal. The STM analysis revealed an adaptation of the conformation of the prochiral building blocks and a site-selectivity of the adsorption. We present a general protocol for testing the suitability of higher-molecular-weight compounds, such as porphyrins, to be deposited on surface by sublimation in ultra-high vacuum (UHV). This protocol combines classical methods of chemical analysis with typical surface science techniques.
- Alberti, Mariza N.,Nowakowska, Sylwia,Tzirakis, Manolis D.,Nowakowski, Jan,Fesser, Petra,Schweizer, W. Bernd,Shchyrba, Aneliia,Thilgen, Carlo,Jung, Thomas A.,Diederich, Fran?ois
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supporting information
p. 5705 - 5719
(2014/10/16)
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- A zinc porphyrin sensitizer modified with donor and acceptor groups for dye-sensitized solar cells
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In this article, we have designed and synthesized a novel donor-π-acceptor (D-π-A) type porphyrin-based sensitizer (denoted UI-5), in which a carboxyl anchoring group and a 9,9-dimethyl fluorene were introduced at the meso-positions of porphyrin ring via phenylethynyl and ethynyl bridging units, respectively. Long alkoxy chains in ortho-positions of the phenyls were supposed to reduce the degree of dye aggregation, which tends to affect electron injection yield in a photovoltaic cell. The cyclic voltammetry was employed to determine the band gap of UI-5 to be 1.41 eV based on the HOMO and LUMO energy levels, which were estimated by the onset oxidation and reduction potentials. The incident monochromatic photon-to-current conversion efficiency of the UI-5 DSSC assembled with double-layer (20 nm-sized TiO2/400 nm-sized TiO2) film electrodes appeared lower upon overall ranges of the excitation wavelengths, but exhibited a higher value over the NIR ranges (λ = 650-700 nm) compared to the common reference sensitizer N719. The UI-5-sensitized cell yielded a relatively poor device performance with an overall conversion efficiency of 0.74% with a short circuit photocurrent density of 3.05 mA/cm2, an open circuit voltage of 0.54 mV and a fill factor of 0.44 under the standard global air mass (AM 1.5) solar conditions. However, our report about the synthesis and the photovoltaic characteristics of a porphyrin-based sensitizer in a D-π - A structure demonstrated a significant complex relationship between the sensitizer structure and the cell performance.
- Lee, Seewoo,Sarker, Ashis K.,Hong, Jong-Dal
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p. 3052 - 3058
(2014/12/11)
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