- Platinum(II) Ring-Fused Chlorins as Near-Infrared Emitting Oxygen Sensors and Photodynamic Agents
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Novel near-infrared luminescent compounds based on platinum(II) 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused chlorins are described. These compounds have high photostability and display light emission, in particular simultaneous fluorescence and phosphorescence emission in solution at room temperature, in the biologically relevant 700-850 nm red and near-infrared (NIR) spectral region, making them excellent materials for biological imaging. The simultaneous presence of fluorescence and phosphorescence emission at room temperature, with the phosphorescence strongly quenched by oxygen whereas fluorescence remains unaffected, allows these compounds to be used as ratiometric oxygen sensors in chemical and biological media. Both steady-state (fluorescence vs phosphorescence intensities) and dynamic (dependence of phosphorescence lifetimes upon oxygen concentration) luminescence approaches can be used. Photocytotoxicity studies against human melanocytic melanoma cells (A375) indicate that these compounds display potential as photosensitizers in photodynamic therapy.
- Pereira, Nelson A. M.,Laranjo, Mafalda,Casalta-Lopes, Jo?o,Serra, Arménio C.,Pi?eiro, Marta,Pina, Jo?o,Seixas de Melo, J. Sérgio,Senge, Mathias O.,Botelho, M. Filomena,Martelo, Liliana,Burrows, Hugh D.,Pinho E Melo, Teresa M. V. D.
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- The synthesis of 5,10,15,20-tetraarylporphyrins and their platinum(II) complexes as luminescent oxygen sensing materials
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5,10,15,20-tetraarylporphyrins TPP, TNP and TPyP (where TPP = 5,10,15,20-tetraphenylporphyrin, TNP = 5,10,15,20-tetranaphthalporphyrin and TPyP = 5,10,15,20-tetrapyrenyl-porphyrin) and the corresponding Pt(II) complexes were prepared. The photophysical pr
- Wu, Wenting,Wu, Wanhua,Ji, Shaomin,Guo, Huimin,Wang, Xin,Zhao, Jianzhang
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- Metallated porphyrin noncovalent interaction with reduced graphene oxide-modified electrode for amperometric detection of environmental pollutant hydrazine
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A reduced graphene oxide/platinum(II) tetraphenylporphyrin nanocomposite (RGO/Pt-TPP)-modified glassy carbon electrode was developed for the selective detection of hydrazine. The RGO/Pt-TPP nanocomposite was successfully prepared via noncovalent π–π stack
- Sakthinathan, Subramanian,Kubendhiran, Subbiramaniyan,Chen, Shen-Ming,Govindasamy, Mani,Al-Hemaid, Fahad M.A.,Ajmal Ali,Tamizhdurai,Sivasanker
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- Platinum(II) ring-fused chlorins as efficient theranostic agents: Dyes for tumor-imaging and photodynamic therapy of cancer
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The discovery of Pt-chlorin-type theranostic agents is described. Luminescent Pt(II) 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused chlorins, with different degrees of hydrophilicity, have been synthesized and their in vitro photocytotoxicity against human melanoma, oesophageal and bladder carcinomas was studied. A di(hydroxymethyl)-substituted chlorin was identified as a privileged molecule to explore imaging-guided photodynamic therapy. In addition to the high activity as PDT agent and absence of cytotoxicity per se, this molecule showed the ideal photophysical and photochemical properties. In vivo studies using a A375 melanoma mouse model, proved the extraordinary properties of this chlorin as a luminescent probe and the ability to impair tumor growth, making image guided treatment and follow up a possibility.
- Botelho, Maria Filomena,Brito, Ana F.,Laranjo, Mafalda,Nascimento, Bruno F. O.,Pereira, Nelson A. M.,Pineiro, Marta,Pinho e Melo, Teresa M. V. D.,Sarmento-Ribeiro, Ana Bela,Aguiar, Márcia Campos,Brites, Gon?alo,Casalta-Lopes, Jo?o,Gon?alves, Ana Cristina
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- Observations on the Mechanochemical Insertion of Zinc(II), Copper(II), Magnesium(II), and Select Other Metal(II) Ions into Porphyrins
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Building on a proof of concept study that showed the possibility of the mechanochemical insertion of some M(II) metals into meso-tetraphenylporphyrin using a ball mill as an alternative to traditional solution-based methods, we present here a detailed study of the influence of the many experimental variables on the reaction outcome performed in a planetary mill. Using primarily the mechanochemical zinc, copper, and magnesium insertion reactions, the scope and limits of the type of porphyrins (electron-rich or electron-poor meso-tetraarylporphyrins, synthetic or naturally occurring octaalkylporphyrins, and meso-triphenylcorrole) and metal ion sources suitable for this metal insertion modality were determined. We demonstrate the influence of the experimental metal insertion parameters, such as ball mill speed and reaction time, and investigated the often surprising roles of a variety of grinding agents. Also, the mechanochemical reaction conditions that remove zinc from a zinc porphyrin complex or exchange it for copper were studied. Using some standardized conditions, we also screened the feasibility of a number of other metal(II) insertion reactions (VO, Ni, Fe, Co, Ag, Cd, Pd, Pt, Pb). The underlying factors determining the rates of the insertion reactions were found to be complex and not always readily predictable. Some findings of fundamental significance for the mechanistic understanding of the mechanochemical insertion of metal ions into porphyrins are highlighted. Particularly the mechanochemical insertion of Mg(II) is a mild alternative to established solution methods. The work provides a baseline from which the practitioner may start to evaluate the mechanochemical metal insertion into porphyrins using a planetary ball mill.
- Atoyebi, Adewole O.,Brückner, Christian
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supporting information
p. 9631 - 9642
(2019/03/26)
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- PLATINUM(II) RING-FUSED CHLORINS, METHODS AND USES THEREOF
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The present disclosure relates derivatives of platinum (II) ring-fused chlorins with a general formula I or II, more particularly derivatives, which are novel and stable near infrared luminescent compounds for imaging, sensing, optoelectronics application
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Paragraph 0087
(2017/09/21)
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- Design of oxygen sensing nanomaterial: Synthesis, encapsulation of phenylacetylide substituted Pd(II) and Pt(II) meso-tetraphenylporphyrins into poly(1-trimethylsilyl-1-propyne) nanofibers and influence of silver nanoparticles
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Room temperature phosphorescent oxygen sensors have been designed by embedding symmetric palladium(ii) or platinum(ii) meso-tetraphenylporphyrins in poly(1-trimethylsilyl-1-propyne) in the form of nanofibers along with/without silver nanoparticles. These materials combine the advantages of the high oxygen sensitivity of porphyrins and the enhanced surface area of porous nanofibers. Phenylacetylide bearing palladium(ii) or platinum(ii) meso-tetraphenylporphyrins (Pd-TPA, Pt-TPA, Pd-TPP and Pt-TPP) were designed to enhance phosphorescence quantum yields as well as sensitivity towards oxygen. Their syntheses were achieved by 2 alternative methods including successive metallation reactions and Sonogashira coupling via optimization of the synthetic strategies and conditions. The respective effect of the metal (Pd or Pt) and substituent on phosphorescence quantum yield as well as other photophysical properties was considered. The sensing performances of the corresponding silver-free and silver doped nanofibers were tested in the oxygen concentration range of 0.0-100.0%. The offered composites provided the advantages of fast response, enhanced sensitivity, reversible and long lasting response, higher Stern-Volmer constants (KSV) and low limit of detection values extending to 7.5 ppm for oxygen.
- ?nal, Emel,Ay, Zeynep,Yel, Zübeyde,Ertekin, Kadriye,Gürek, Ay?e Gül,Topal, Sevinc Zehra,Hirel, Catherine
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p. 9967 - 9977
(2016/02/05)
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- Facile and practical synthesis of platinum(II) porphyrins under mild conditions
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A facile and mild method for the preparation of platinum(II) porphyrin complexes is reported. A simple treatment of freebase porphyrins with 1.5 equiv of [PtCl2(PhCN)2] in the presence of sodium propionate in refluxing chlorobenzene (bp: 131°C) affords the corresponding Pt(II) complexes in good yields within a few hours. Furthermore, the work-up processes for our methods are less complex than those for the reported ones because chlorobenzene can be easily removed by simple evaporation.
- Yamashita, Ken-Ichi,Katsumata, Natsuki,Tomita, Shohei,Fuwa, Miki,Fujimaki, Keisuke,Yoda, Takuya,Hirano, Daisuke,Sugiura, Ken-Ichi
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p. 492 - 494
(2015/05/27)
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- Hydrogen bond controlled formation of trans-dihydroxo porphyrinato platinum(IV) complexes: Synthesis, characterization and catalytic activity in olefin epoxidation
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A number of trans-dihydroxo porphyrinato platinum(IV) complexes, [(porp)PtIV(OH)2] have been synthesized and characterized from their platinum(II)-porphyrin precursors by spectroscopic methods. The crystal structure of the platinum complex of trans-dihydroxo-meso-tetramesitylporphyrinato platinum(IV) meta-chlorobenzoic acid ([(TMP)PtIV(OH)2](m-CBA)2) has also been determined. The porphyrin periphery is planar and the platinum atom has a slightly distorted octahedral environment. It must be noted that there is a very strong O-H?O hydrogen bond between the hydrogen atoms of m-chlorobenzoic acids and the two hydroxo ligands coordinated to the platinum center. This crystal structure has been previously described by us as trans-dihydroxo-meso-tetramesitylporphyrinato platinum(VI) meta-chlorobenzoate ([(TMP)PtVI(OH)2](m-CB)2), but the spectroscopic data has been reinterpreted due to the contradictory +6 oxidation state for platinum. The UV-Vis and NMR spectroscopic data suggest that the porphyrin skeleton is similar to that of normal porphyrins and are also indicative of the +4 oxidation state for platinum. Cyclic voltammetry studies also indicate that PtIITMP can oxidize up to PtIV(TMP+) species via three successive one-electron oxidation steps. The results of DFT studies and NBO analysis confirm that platinum has +4 oxidation state in both [(TMP)Pt(OH)2](m-CBA)2 and [(TMP)Pt(OH)2](m-CB)2 complexes. The catalytic activity of these porphyrin complexes has been investigated for the oxidation of various alkenes in the presence of iodosylbenzene.
- Alemohammad, Tahereh,Safari, Nasser,Rayati, Saeed,Gheidi, Mahin,Mortazavimanesh, Anahita,Khavasi, Hamidreza
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p. 198 - 208
(2015/06/23)
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- Protecting the triplet excited state in sterically congested platinum porphyrin
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Platinum tetrakis(2,4,6-triethylphenyl)porphyrin (Pt-1) was synthesized and its structural (X-ray), electrochemical and photophysical properties were fully characterized. Comparative studies of Pt-1 and its unsubstituted analog PtTPP show the effect of sterically congesting ortho-substituents on the dynamics of the triplet excited states. Lowered quenching rates by 3-4 times were observed for Pt-1vs. PtTPP in the presence of oxygen and perylene, and in concentration (self)-quenching experiments.
- Moiseev,Margulies,Schneider,Belanger-Gariepy,Perepichka
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supporting information
p. 2676 - 2683
(2014/02/14)
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- Synthesis and properties of ms- and β-substituted Pt(II) and Pt(IV) tetraphenylporphyrinates
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The interaction of 5,10,15,20-tetraphenylporphyrin, 5,10,15,20-tetra-(4- chlorophenyl)porphyrin, 2-bromo-5,10,15,20-tetraphenylporphyrin, and 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrin with platinum(II) chloride in boiling phenol has been studie
- Chizhova,Kulikova,Mamardashvili
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p. 2108 - 2111
(2014/01/17)
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- Dicationic platinum porphyrin catalyzed cycloisomerization of enynes
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Cycloisomerization of 1,6-enynes is successfully carried out in the presence of a dicationic platinum(IV) catalyst to afford five-membered ring systems. The use of a weakly coordinating axial ligand is the key to bringing out the catalytic activity of platinum porphyrin for the reaction.
- Hasegawa, Makoto,Kurahashi, Takuya,Matsubara, Seijiro
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supporting information
p. 6196 - 6198
(2013/10/22)
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- A robust palladium(II)-Porphyrin complex as catalyst for visible light induced oxidative C-H functionalization
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A series of palladium(II)-porphyrin complexes that display dual emissions with lifetimes up to 437μs have been synthesized. Among the four complexes, PdF20TPP is an efficient and robust catalyst for photoinduced oxidative C-H functionalization by using oxygen as terminal oxidant. α-Functionalized tertiary amines were obtained in good to excellent yields by light irradiation (λ>400nm) of a mixture of PdF20TPP, tertiary amine, and nucleophile (cyanide, nitromethane, dimethyl malonate, diethyl phosphite, and acetone) under aerobic conditions. Four examples of intramolecular cyclized amine compounds could be similarly prepared. Comparison of the UV-visible absorption spectra before and after the photochemical reaction revealed that PdF20TPP was highly robust (>95 % recovery). The practical application of PdF20TPP has been revealed by the photochemical reactions performed by using a low catalyst loading (0.01mol %) and on a 10mmol scale. The PdF20TPP catalyst could sensitize photoinduced oxidation of sulfides to sulfoxides in excellent yields. Mechanistic studies revealed that the photocatalysis proceeded by singlet-oxygen oxidation. Long-lived excited states! A series of palladium(II)-porphyrin complexes have been synthesized and found to display long-lived excited states with lifetimes up to 437μs (see scheme). Among these complexes, PdF 20TPP is an efficient and robust catalyst for a broad array of photoinduced oxidative C-H functionalization reactions. PtF20TPP= platinum(II) meso-tetrakis(2,3,4,5,6-pentafluorophenyl)porphyrin.
- To, Wai-Pong,Liu, Yungen,Lau, Tai-Chu,Che, Chi-Ming
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p. 5654 - 5664
(2013/06/04)
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- Turn on fluorescence sensing of vapor phase electron donating amines via tetraphenylporphyrin or metallophenylporphrin doped polyfluorene
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A sensitive, selective, reversible, and easy performance way of detecting electron donating volatile amines such as abused drug methamphetamine (MAPA) has been developed.
- He, Chao,He, Qingguo,Deng, Changmin,Shi, Liqi,Zhu, Defeng,Fu, Yanyan,Cao, Huimin,Cheng, Jiangong
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supporting information; experimental part
p. 7536 - 7538
(2010/12/19)
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- Microwave-promoted insertion of Group 10 metals into free base porphyrins and chlorins: Scope and limitations
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The scope and limitations of microwave heating as a tool for insertion of Group 10 metals into meso-tetraphenyl-porphyrin, -porpholactone, and -2,3-dihydroxychlorin derivatives are discussed. In some cases it is possible to reduce reaction times dramatically while obtaining good yields of the metallated products while in others new issues arise relating to the metal salt used as well as acceleration not only of the metallation reaction but also of byproduct formation. The Royal Society of Chemistry.
- Dean, Michelle L.,Schmink, Jason R.,Leadbeater, Nicholas E.,Brueckner, Christian
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p. 1341 - 1345
(2008/09/20)
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- Effect of the chemical modification of the tetrapyrrole macrocycle on the reactivity of porphyrins in complexation with Pt4+ and Pd 2+ cations
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The reactions of 5,10,15,20-tetraphenylporpine, 5,10,15-triphenyl-20-(4- hexadecanoxyphenyl)porphine, 5,10,15,20-tetra-(4-butoxyphenyl)porphine, and 2,3,7,8,12,13,17,18-ocaethylporphine with H2PtCl6 in boiling phenol and with PdCl2 in boiling dimethylformamide are studied by spectrophotometry. Due to a strong electronic effect of the substituents, the reactivity of the tetrapyrrole macrocycle during porphyrinate formation changes by more than two orders of magnitude. Platinum(II) 5,10,15-triphenyl-20-(4-hexadecanoxyphenyl)porphinate and palladium(II) 5,10,15,20-tetra-(4-butoxyphenyl)porphinate have been synthesized and identified for the first time. Nauka/Interperiodica 2007.
- Chizhova,Mamardashvili
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p. 250 - 253
(2008/10/09)
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- Porphyrin Complexes of Platinum(II), Platinum(III), and Platinum(IV): Synthesis and Properties
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Complexing mesotetraphenylporphine H2TPP with K2[PtCl6] in boiling pyridine or with K2[PtCl4] in boiling benzonitrile produces stable platinum complexes of composition (Cl)2PtIVTPP or PtIIITPP. Reacting mesoporphyrin dimethyl ether H2MP with K2[PtCl6] in boiling pyridine yields (Cl)PtIIIMP, a complex in which platinum has an unusual oxidation number. The complexes are identified using UV and IR spectroscopy, by atomic adsorption spectrometry, and by quantitative analysis. The species of the complexes existing in mixed H2SO4-containing proton-donating solvents are discovered. The kinetics of the dissociation of metal porphyrins for various solvent acidities and temperatures are determined. The complexes are soluble in concentrated H2SO4 in the molecular form or in the form of an ion-molecule association species with the proton of the solvent. The stability, solute species, and the mechanism of dissociation of the metal porphyrin are controlled by the presence or absence of an acido ligand in the first coordination sphere and by the configuration of the macrocycle.
- Tyulyaeva,Lomova,Andrianova
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p. 371 - 375
(2008/10/08)
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- Platinum(IV) tetraphenylporphyrin dibromide complexes: Synthesis, characterization, and electrochemistry
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Platinum(IV) porphyrins of the type [Pt(IV) (p-X)4TPP]Br2 where (p-X)4TPP is a para-substituted tetraphenylporphyrin have been synthesized by direct oxidation of their Pt(II) precursors with Br2. Both the Pt(II) and Pt(IV) complexes have been characterized by visible and 1H NMR spectroscopy and their electrochemical properties. In both the oxidation and reduction processes, a substituent effect is evident, and the reduction of Pt(IV) → Pt(II) is identified. The oxidation and reduction potentials of the [Pt(IV) (p-X)4TPP] Br2 complexes are compared to those of the [Pt(II)(p-X)4TPP] precursors and [Pt(IV) (p-X)4TPP]Cl2 analogs. Addition of I2 or I- to Pt(II) porphyrins does not result in oxidative-addition to form Pt(IV) porphyrins. Instead, the addition of I- to [Pt(IV) (p-X)4TPP] Br2 results in the reduction of the platinum to form the corresponding [Pt(II) (p-X)4TPP)]. (C) 2000 Elsevier Science Ltd.
- Mink,Voce,Ingersoll,Nguyen,Boggess,Washburn,Grove
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p. 1057 - 1062
(2008/10/08)
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- CHEMICAL DEGRADATION OF GAS-SENSING MESO-TETRA-ARYLPORPHIN THIN FILMS BY HIGH LEVELS OF DINITROGEN TETROXIDE.
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Thin solid films of free base meso-tetra-arylporphins and their zinc, copper, platinum and palladium complexes have been exposed to high levels of dinitrogen tetroxide (NOX). The optical spectra (300-850 nm) were recorded in transmission before and after
- Honeybourne, Colin L.,Hill, Callum A. S.
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p. 315 - 322
(2008/10/08)
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