DOCSLIB.ORG

Old Dog, New Tricks: Innocent, Five-Coordinate Cyanocobalt Corroles

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Old Dog, New Tricks: Innocent, Five-Coordinate Cyanocobalt Corroles Old Dog, New Tricks: Innocent, Five-coordinate Cyanocobalt Corroles W Osterloh, Nicolas Desbois, Valentin Quesneau, Stéphane Brandès, Paul Fleurat-Lessard, Yuanyuan Fang, Virginie Blondeau-Patissier, Roberto Paolesse, Claude P Gros, Karl M Kadish To cite this version: W Osterloh, Nicolas Desbois, Valentin Quesneau, Stéphane Brandès, Paul Fleurat-Lessard, et al.. Old Dog, New Tricks: Innocent, Five-coordinate Cyanocobalt Corroles. Inorganic Chemistry, American Chemical Society, 2020, 59 (12), pp.8562-8579. 10.1021/acs.inorgchem.0c01037. hal-03198113 HAL Id: hal-03198113 https://hal.archives-ouvertes.fr/hal-03198113 Submitted on 7 May 2021 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Distributed under a Creative Commons Attribution| 4.0 International License Old Dog, New Tricks: Innocent, Five-coordinate Cyanocobalt Corroles W. Ryan Osterloh, Nicolas Desbois, Valentin Quesneau, Stephané Brandes,̀ Paul Fleurat-Lessard, Yuanyuan Fang, Virginie Blondeau-Patissier, Roberto Paolesse,* Claude P. Gros,* and Karl M. Kadish* ABSTRACT: Three mono-CN ligated anionic cobalt A3-triarylcorroles were synthesized and investigated as to their spectroscopic and electrochemical properties in CH2Cl2, pyridine (Py), and dimethyl sulfoxide (DMSO). The newly synthesized corroles provide the first examples of air-stable cobalt corroles with an anionic axial ligand and are represented III − + as [(Ar)3CorCo (CN)] TBA , where Cor is the trivalent corrole macrocycle, Ar is p-(CN)Ph, p-(CF3)Ph, or p-(OMe)Ph, and TBA+ is the tetra-n-butylammonium (TBA) cation. Multiple redox reactions are observed for each mono-CN derivative with a key feature being a more facile first oxidation and a more difficult first reduction in all three solvents as compared to all previously examined corroles with similar meso- and β-pyrrole substituents. Formation constants (log K) for conversion of the five-coordinate mono-CN complex to its six-coordinate bis-CN form ranged from 102.8 for Ar = p-(OMe)Ph to 104.7 for Ar = p-(CN)Ph in DMSO as determined by spectroscopic methodologies. The in situ generated bis-CN complexes, represented as [(Ar)3CorCoIII(CN)2]2−(TBA+)2, and the mixed ligand complexes, represented as [(Ar)3CorCoIII(CN) (Py)]−TBA+, were also investigated as to their electrochemical and spectroscopic properties. UV−visible spectra and electrode reactions of the synthesized mono-CN derivatives are compared with the neutral mono-DMSO cobalt corrole complexes and the in situ generated bis-CN and bis-Py complexes, and the noninnocent (or innocent) nature of each cobalt corrole system is addressed. The data demonstrate the ability of the CN− axial ligand(s) to stabilize the high-valent forms of the metallocorrole, leading to systems with innocent macrocyclic ligands. Although a number of six-coordinate cobalt(III) corroles with N-donor ligands were characterized in the solid state, a dissociation of one axial ligand readily occurs in nonaqueous solvents, and this behavior contrasts with the high stability of the currently studied bis-CN adducts in CH2Cl2, pyridine, or DMSO. Linear free energy relationships were elucidated between the meso-phenyl Hammett substituent constants (Σσ) and the measured binding constants, the redox potentials, and the energy of the band positions in the mono- CN and bis-CN complexes in their neutral or singly oxidized forms, revealing highly predictable trends in the physicochemical properties of the anionic corroles. INTRODUCTION The electrochemical and spectroscopic properties of numerous significantly easier to reduce than innocent macrocyclic corroles possessing a wide variety of meso- and β-pyrrole systems having the same formal oxidation state of the central − substituents have been reported over the last three decades.1 8 metal ion, thus providing insights into the electronic Many of these reports have focused on the use of these configuration of the molecule. compounds for applications as redox and bioinspired Numerous four- and five-coordinate metallocorroles with − − catalysts9 25 or sensors,26 36 with the focal point of cobalt copper, cobalt, and iron have been shown to possess an − corrolate application involving oxygen reduction12,23 25 and oxidized corrole ligand and a reduced metal ion,1−3,26 and − carbon monoxide detection.31 36 Moreover, a particular these complexes were assigned as having a noninnocent emphasis of corrole research has been placed on unveiling macrocyclic ligand in its cation-radical (Cor•2−) form rather 4,37−40 the electronic configuration of the molecule to aid in the than the formal trivalent Cor3− anion. Many of these design of new catalysts.41 The propensity of the corrole macrocycle to behave as a noninnocent ligand under specific conditions has often hindered the ability to definitively assign an exact metal and ligand oxidation state, but published reports from our laboratory2,18,42−50 and others13,21,26,37,38,51−55 have clearly demonstrated that noninnocent corrole macrocycles are 1 Chart 1. Structures and Numbering of Investigated Cobalt Triarylcorroles with p-(CN)Ph, p-(CF3)Ph, or p-(OMe)Ph meso- Substituents complexes with noninnocent macrocycles have also been •−II (Ar)3 Cor Co (DMSO)+ CN shown to undergo multiple reductions and oxidations in III − nonaqueous media, and a conversion between the different F [](Ar)3 CorCo (CN)+ DMSO (3) oxidation states of both the central metal ion and the corrole macrocyclic ligand is easily achieved through either electro- III − − [](Ar)3 CorCo (CN)+ CN chemical or synthetic methods,37,42,56 consequently leading to III 2− a shift from a noninnocent to an innocent metallocorrole F[](Ar)3 CorCo (CN)2 (4) system. fi Both direct and indirect spectroscopic criteria, such as X-ray The nal in situ generated bis-CN adducts in eq 4 were remarkably stable, independent of the Ar group on the corrole, absorption spectroscopy (XAS), electron paramagnetic reso- and exhibited the most-facile oxidation and most difficult nance spectroscopy, and UV−visible spectroscopy, laid out by 57 reduction of any cobalt corrole system investigated. Ganguly and Ghosh have been used to classify ligand After publication of our initial report on anion interaction noninnocence. In our own reports, we established an with cobalt corroles47 we attempted to isolate bis-CN electrochemical litmus test, where the existence of extremely derivatives in the solid state for further analysis but obtained, facile reductions (∼0.00 to −0.20 V vs saturated calomel in each case, only the mono-CN complexes, three of which are electrode (SCE)) for transition-metal corroles can be used as characterized in the current study. The chemical properties of one criterion to establish the presence of a noninnocent ligand these species are described on the following pages and in the case of metallocorroles with iron, cobalt, nickel, or 2,43,45,47−49 compared to the mono-DMSO precursors, [(Ar) CorCo- copper. For example, in the case of cobalt 3 (DMSO)],47 the corresponding in situ generated bis-CN and triarylcorroles, the four-coordinate complexes are reduced at bis-Py adducts, as well as the transient mixed-ligand adducts the macrocycle (eq 1), while the six-coordinate species are containing one CN− and one pyridine axial ligand. The mono- reduced at the central metal ion (eq 2), giving, in both cases, and bis-cyanocobalt complexes are the first known examples of the same cobalt(II) reduction product. air-stable cobalt corroles with anionic axial ligands and are •− − n− + II II represented as [(Ar)3CorCo(CN)n] (TBA )n, where Cor is (Ar)3 Cor Co+[ eF (Ar)3 CorCo ] (1) the trivalent corrole macrocycle, Ar is p-(CN)Ph, p-(CF3)Ph, or p-(OMe)Ph, and n = 1 or 2, as shown in Chart 1. TBA+ is III +[−−II ]+ (Ar)3 CorCo (L)23 eF (Ar) CorCo 2L (2) the tetra-n-butylammonium (TBA) cation. fi II − Although the same nal [(Ar)3CorCo ] product is formed EXPERIMENTAL SECTION in both cases, the difference in thermodynamic half-wave potentials for the one-electron addition can be significant, Materials and Instrumentation. All chemicals and solvents were of the highest electrochemical grade available and were used without varying by as much as 1.0 V depending on the type of axial fi ≥ fi 38,48,58 further puri cation. Anhydrous dichloromethane (CH2Cl2, 99.8%), ligand and speci c Ar substituents. ≥ ff anhydrous dimethyl sulfoxide (DMSO, 99.9%), and anhydrous One problem with elucidating the e ect of axial coordina- pyridine (Py, ≥99.8%) were purchased and used as received. Tetra-n- tion on the redox potentials of hexacoordinate cobalt corroles butyl-ammonium perchlorate (TBAP, ≥99.0%) and 95.0% tetra-n- is the lability of the axial ligand(s) in solution, which results in butyl-ammonium cyanide (TBACN) were purchased from Sigma a concentration-dependent complexation where one, or both, Chemical Co. and stored in a desiccator until used. ligands dissociate in dilute solutions. In search of nonlabile NMR solvents were purchased from Eurisotope and were used coordinating ligands, we recently investigated the possible without further purification. 1H NMR spectra were recorded on a binding of anionic ligands to neutral cobalt triarylcorroles and Bruker Avance III 500 spectrometer operating at 500 MHz and − available at the PACSMUB-WPCM technological platform, which found that 10 of the 11 investigated anionic ligands (PF6 , − − − − − − − − − relies on the “Institut de Chimie Moleculairé de l’Université de BF4 , HSO4 , ClO4 ,Br,I,Cl, OAc ,F, OTs ) were Bourgogne” and SATT SAYENS “TM”, a Burgundy University private unable to bind to the cobalt center of the neutral complex, with 1 − subsidiary.
Load more

Recommended publications
  • Synthesis and Spectroscopic Properties of Β-Meso Directly Linked Porphyrin–Corrole Hybrid Compounds
    Synthesis and spectroscopic properties of β-meso directly linked porphyrin–corrole hybrid compounds Baris Temelli* and Hilal Kalkan Full Research Paper Open Access Address: Beilstein J. Org. Chem. 2018, 14, 187–193. Hacettepe University, Department of Chemistry, Beytepe Campus, doi:10.3762/bjoc.14.13 06800, Ankara, Turkey Received: 09 October 2017 Email: Accepted: 05 January 2018 Baris Temelli* - [email protected] Published: 22 January 2018 * Corresponding author Associate Editor: J. Aubé Keywords: © 2018 Temelli and Kalkan; licensee Beilstein-Institut. corrole; hybrid compounds; indium(III) chloride; porphyrin; License and terms: see end of document. porphyrinoids Abstract The preparation of β-meso directly linked porphyrin–corrole hybrids was realized for the first time via an InCl3-catalyzed condensa- tion reaction of 2-formyl-5,10,15,20-tetraphenylporphyrins with meso-substituted dipyrromethanes. Hybrid compounds have been characterized by 1H NMR, 13C NMR, 2D NMR, UV–vis absorption and fluorescence spectroscopy. Introduction Porphyrins and metalloporphyrins play an important role in compounds, corroles, contracted porphyrin analogues [31-33], chemistry, biology, medical and materials sciences because of assumed an important place in porphyrin chemistry due to their their presence in biological compounds such as chlorophyll and small cavities, trianionic characters, high fluorescence quantum heme molecules that have very important functions in the yields and favorable electronic properties. Porphyrin–corrole metabolism of living organisms [1,2]. In recent years, efforts in conjugates have been successfully used as donor–acceptor porphyrin chemistry have been focused on the synthesis of systems in photoinduced charge separation processes. It was multichromophore containing compounds and their potential shown that derivatives of these conjugates could be potentially applications in molecular wires, sensors, nonlinear optical used in photovoltaic applications [21-23].
    [Show full text]
  • 1 INTRODUCTION Corroles Are Tetrapyrrolic Molecules, Maintaining
    1 Chapter 1 INTRODUCTION Corroles are tetrapyrrolic molecules, maintaining the skeletal structure of corrin, with its three meso carbon positions and one direct pyrrole-pyrrole linkage, and possessing the aromaticity of porphyrins (see figure 1.1). First reported by Johnson and Kay in 1965[1], corroles were the end product of a many step synthetic scheme, finally being formed by the photocyclization of a,c-biladienes. While this last step was simple, with 20-60% yields, the route to a,c-biladienes was far from easy. Indeed, the overall reaction from readily available starting materials to corrole was a multi-step synthesis, with poor yields in many of the reactions. Thus, while corroles have been known for more than 40 years, research in the field was slow to progress. It wasn’t until the discovery of new synthetic methods for corroles developed in 1999 by different groups working independently that research in this area really started to expand[2]. This is not to say, however, that the field of corrole research was non-existent prior to the development of the new methodologies. While it was slow growing after the initial publication, it was far from stagnant, and many of the interesting properties of corroles were investigated by different groups. Among these properties is their ability to stabilize unusually high formal oxidation states of metal ions, such as iron(IV), cobalt(IV), and cobalt(V)[3, 4]. In fact, one particular corrole available through a method developed by Zeev 2 N N H N N H H N N N N a b N N H H H N N c Figure 1.1.
    [Show full text]
  • Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Люминесцентные Свойс
    Porphyrins Paper Порфирины Статья DOI: 10.6060/mhc170621r Luminescence Features of Neodymium(III) Compounds with Various Tetrapyrrole Macrocycles Nikolay N. Semenishyn,a Sergii S. Smola,a Natalya V. Rusakova,a@ Gerbert L. Kamalov,a Yulia G. Gorbunova,b,c and Aslan Yu. Tsivadzeb,c aA.V. Bogatsky Physico-Chemical Institute, 65080 Odessa, Ukraine bA.N. Frumkin Institute of Physical Chemistry and Electrochemistry of Russian Academy of Sciences, 119071 Moscow, Russia cN.S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences, 119991 Moscow, Russia @Corresponding author E-mail: [email protected] We considered the changes in the luminescent properties in the series of neodymium(III) complexes of various coordination types with different tetrapyrrole macrocycles (porphyrins, phthalocyanines and corroles): mono- nuclear complexes (metal-ligand ratio 1:1), sandwich type complexes (metal-ligand ratio 1:2 or 2:3), peripheral binding (on the basis of ditopic tetrapyrrole, metal-ligand ratio 1:1). 4f-Luminescence in the near infrared region is observed in all studied Nd-complexes as a result of intramolecular transfer of excitation energy. Each kind of com- plexes has its unique features, which are discussed. The peripheral complexes are dual-emissive: they display both neodymium(III) 4f-emission and molecular fluorescence. The values of quantum yield of molecular fluorescence as well as 4f-luminescence are estimated. It was found that binding type plays a key role in excited state relaxation pathways in the molecule. Corroles have unusual behaviour in terms of Nd sensitization. Keywords: Tetrapyrroles, luminescence, neodymium, porphyrin, phthalocyanine, corrole. Люминесцентные свойства соединений неодима(III) с различными тетрапиррольными макроциклами Н.
    [Show full text]
  • 5 SYNTHESES While the Initial Synthesis of Corroles Was a Very Long Procedure, the Advent of a One Pot Synthesis by Gross and Co
    5 Chapter 2 SYNTHESES While the initial synthesis of corroles was a very long procedure, the advent of a one pot synthesis by Gross and co-workers in 1999 revolutionized the process of making corroles. It is now possible to make hundreds of milligrams of free-base corrole in a single day, compared to weeks or even months of work with the previous methods. Detailed in this chapter are the synthetic methods used for the corroles studied in this work, including two different free-bases; gallium, manganese, and tin complexes of these free-bases; and work done toward the synthesis of an indium corrole. The particular corrole free-bases used in this study were 5,10,15- tris(pentafluorophenyl)corrole, and 2,17-bis(sulfonato)-5,10-15- tris(pentafluorophenyl)corrole. The structures for these two molecules are shown in figure 2.1. General Synthetic Procedures All corroles used in this work are derived from the first of these, 5,10,15- tris(pentafluorophenyl)corrole (1), which in turn is synthesized from pyrrole and pentafluorobenzaldehyde. This can be accomplished by different methods, either involving a solid support, an acid to aid the reaction, or neat. All three methods will be described at the end of this chapter. However, in all cases, the synthesis of 1 is a condensation reaction 6 a b C6F5 C6F5 N N N N H H C F C F C F 6 5 H H 6 5 6 5 H H C6F5 N N N N SO3H SO3H Figure 2.1. Structures of the two free-base corroles used in this study.
    [Show full text]
  • Triphenylamine Corrole Dyads: Synthesis, Characterization and Substitution Effect on Photophysical Properties
    J. Chem. Sci. Vol. 129, No. 2, February 2017, pp. 223–237. c Indian Academy of Sciences. DOI 10.1007/s12039-016-1219-5 REGULAR ARTICLE Triphenylamine corrole dyads: Synthesis, characterization and substitution effect on photophysical properties KOLANU SUDHAKAR and LINGAMALLU GIRIBABU∗ Inorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka, Hyderabad, Telangana, 500 007, India Email: [email protected] MS received 10 November 2016; revised 7 December 2016; accepted 8 December 2016 Abstract. We present our results on the effect of substitution on the photophysical properties of donor- acceptor (D-A) systems in which triphenylamine is the donor and substituted corroles i.e., 5,15-phenyl-10- triphenylaminecorrole TPACor 1, 5,15-di(3,5-ditertbutylphenyl)-10-triphenylaminecorrole TPACor 2, and 5,15-(4-nitrophenyl)-10-triphenylaminecorrole TPACor 3 is the acceptor. All three dyads have been character- ized by elemental analysis, MALDI-MS, cyclic voltammetry, UV-Vis and fluorescence (steady state and time- resolved) spectroscopies. Both Soret and Q bands of TPACor 3 are red-shifted when compared to other two dyads due to the presence of electron withdrawing nitro group. Similarly, redox properties of TPACor 3 are altered, when correlated to TPACor 1 and TPACor 2 dyads. However, the fluorescence emission of tripheny- lamine in all three dyads was quenched significantly (>90%) compared to its monomeric unit. The presence of either electron releasing or electron withdrawing group on corrole moiety has not much effect on the photo- physical properties. The quenched emission was attributed to intramolecular excitation energy transfer and the photoinduced electron transfer reactions contested in these dyads.
    [Show full text]
  • A Biomimetic Copper Corrole
    A Biomimetic Copper Corrole – Preparation, Characterization, and Reconstitution with Horse Heart Apomyoglobin Martin Bröring, Frédérique Brégier, Burghaus Olaf, Christian Kleeberg To cite this version: Martin Bröring, Frédérique Brégier, Burghaus Olaf, Christian Kleeberg. A Biomimetic Copper Corrole – Preparation, Characterization, and Reconstitution with Horse Heart Apomyoglobin. Journal of Inorganic and General Chemistry / Zeitschrift für anorganische und allgemeine Chemie, Wiley-VCH Verlag, 2010, 636 (9-10), pp.1760. 10.1002/zaac.201000102. hal-00552467 HAL Id: hal-00552467 https://hal.archives-ouvertes.fr/hal-00552467 Submitted on 6 Jan 2011 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. ZAAC A Biomimetic Copper Corrole – Preparation, Characterization, and Reconstitution with Horse Heart Apomyoglobin Journal: Zeitschrift für Anorganische und Allgemeine Chemie Manuscript ID: zaac.201000102.R1 Wiley - Manuscript type: Article Date Submitted by the 25-Mar-2010 Author: Complete List of Authors: Bröring, Martin; Philipps-Universität Marburg, Fachbereich
    [Show full text]
  • Corrole Synthesis and Catalytic Applications Toward Cobalt(III)- Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation
    University of South Florida Scholar Commons Graduate Theses and Dissertations Graduate School 12-31-2010 Corrole Synthesis and Catalytic Applications Toward Cobalt(III)- Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation Chung Sik Kim University of South Florida Follow this and additional works at: https://scholarcommons.usf.edu/etd Part of the American Studies Commons, and the Chemistry Commons Scholar Commons Citation Kim, Chung Sik, "Corrole Synthesis and Catalytic Applications Toward Cobalt(III)-Catalyzed Epoxidation, N- H Insertion, and Cyclopropanation" (2010). Graduate Theses and Dissertations. https://scholarcommons.usf.edu/etd/3459 This Dissertation is brought to you for free and open access by the Graduate School at Scholar Commons. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. Corrole Synthesis and Catalytic Applications Toward Cobalt (III)-Catalyzed Epoxidation, N-H Insertion, and Cyclopropanation by Chung Sik Kim A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry College of Arts and Sciences University of South Florida Major Professor: X. Peter Zhang, Ph.D. Jon Antilla, Ph.D. Roman Manetsch, Ph.D. Mark McLaughlin, Ph.D. Date of Approval: Oct 20, 2010 Keywords: Corroles, Cobalt(III) Complex, Epoxidation, N-H Insertion, and Cyclopropanation Copyright © 2010, Chung Sik Kim Special Thanks To my God To my
    [Show full text]
  • Synthesis and Characterization of Meso-Substituted A2B Corroles with Extended P-Electronic Structure
    Monatsh Chem https://doi.org/10.1007/s00706-017-2114-6 ORIGINAL PAPER Synthesis and characterization of meso-substituted A2B corroles with extended p-electronic structure 1 1 2 1 Michael Haas • Sabrina Gonglach • Stefan Mu¨llegger • Wolfgang Scho¨fberger Received: 14 November 2017 / Accepted: 20 November 2017 Ó The Author(s) 2017. This article is an open access publication Abstract We report the chemical synthesis and charac- Keywords A2B corrole Á Pyrene Á terization of the stable 5,15-bis(pentafluorophenyl)-10- Sila-Sonogashira coupling Á p-Conjugation Á Copper Á (trimethylsilylethynyl)corrole which serves as a precursor Electron paramagnetic resonance for the subsequent in situ sila-Sonogashira-cross-coupling reaction and metalation with copper(II) acetate. Under ambient conditions and a common catalyst system the Introduction reaction with 1-iodopyrene occurred within five hours. Due to the direct conjugation of the 18p-electronic system of The establishment of novel synthesis routes towards sym- the corrole macrocycle over the alkynyl group to the pyr- metric and asymmetric corroles increased significantly ene moiety the optical transitions in the Soret (B-) band over the past two decades [1–5]. This trend was triggered Q-band region are significantly altered. The copper corrole by the first published one-pot synthesis of corroles reported exhibited complex hyperfine and superhyperfine structure in 1999 by Gross and Paolesse [6, 7]. Since then, the scope in the EPR spectrum. The assignment of the EPR spectrum of corrole application grew tremendously including reveals the existence of an axial [CuII-cor•?] species. examples in the fields of catalysis, photochemical sensors, Graphical abstract molecular electronics, and biomedicinal applications [8–13].
    [Show full text]
  • And Tris(Pentafluorophenyl))Corrole [Chemistry]
    City University of New York (CUNY) CUNY Academic Works Open Educational Resources LaGuardia Community College 2019 Microwave Solventless Synthesis of Meso-Tetrakis (Pentafluorophenyl)Poprphyrin (TPPF20) and Tris(Pentafluorophenyl))Corrole [Chemistry] Sunaina Singh CUNY La Guardia Community College How does access to this work benefit ou?y Let us know! More information about this work at: https://academicworks.cuny.edu/lg_oers/87 Discover additional works at: https://academicworks.cuny.edu This work is made publicly available by the City University of New York (CUNY). Contact: [email protected] Dr. Sunaina Singh Organic Chemistry I-SCC 251 Biology/Environmental Science Natural Sciences Department, LaGuardia Community College, CUNY Assignment Title: Microwave Solventless Synthesis of Meso-Tetrakis (Pentafluorophenyl)Poprphyrin (TPPF20) and Tris(Pentafluorophenyl))Corrole Organic chemistry is a two-semester course (Organic Chemistry I, SCC 251 and Organic Chemistry II, SCC 252) required for majors in Biology. The SCC 251 course has been designated for the Integrative Learning Core Competency as well the Digital Communication Ability. This course emphasizes the synthesis, structure, reactivity, and mechanisms of reaction of organic compounds. Laboratory stresses various organic synthetic and analytic techniques (distillation, extraction, chromatography and spectroscopy). This lab provided an opportunity for students to go deeper with the chemistry content by correlating to the concepts they learned in General Chemistry courses such as
    [Show full text]
  • Cell-Penetrating Protein/Corrole Nanoparticles Matan Soll1, Tridib K
    www.nature.com/scientificreports OPEN Cell-Penetrating Protein/Corrole Nanoparticles Matan Soll1, Tridib K. Goswami1, Qiu-Cheng Chen 1, Irena Saltsman1, Ruijie D. Teo 3, Mona Shahgholi3, Punnajit Lim 2, Angel J. Di Bilio3, Sarah Cohen1, John Termini2, 3 1 Received: 19 June 2018 Harry B. Gray & Zeev Gross Accepted: 18 December 2018 Recent work has highlighted the potential of metallocorroles as versatile platforms for the development Published: xx xx xxxx of drugs and imaging agents, since the bioavailability, physicochemical properties and therapeutic activity can be dramatically altered by metal ion substitution and/or functional group replacement. Signifcant advances in cancer treatment and imaging have been reported based on work with a water-soluble bis-sulfonated gallium corrole in both cellular and rodent-based models. We now show that cytotoxicities increase in the order Ga < Fe < Al < Mn < Sb < Au for bis-sulfonated corroles; and, importantly, that they correlate with metallocorrole afnities for very low density lipoprotein (VLDL), the main carrier of lipophilic drugs. As chemotherapeutic potential is predicted to be enhanced by increased lipophilicity, we have developed a novel method for the preparation of cell-penetrating lipophilic metallocorrole/serum-protein nanoparticles (NPs). Cryo-TEM revealed an average core metallocorrole particle size of 32 nm, with protein tendrils extending from the core (conjugate size is ~100 nm). Optical imaging of DU-145 prostate cancer cells treated with corrole NPs (≤100 nM) revealed fast cellular uptake, very slow release, and distribution into the endoplasmic reticulum (ER) and lysosomes. The physical properties of corrole NPs prepared in combination with transferrin and albumin were alike, but the former were internalized to a greater extent by the transferrin-receptor-rich DU-145 cells.
    [Show full text]
  • Synthesis and Characterization of Metallocorrole Complexes By
    Synthesis and Characterization of Metallocorrole Complexes By Heather Louisa Buckley A dissertation submitted in partial satisfaction of the requirements for the degree of Doctor of Philosophy in Chemistry in the Graduate Division of the University of California, Berkeley Committee in charge: Professor John Arnold, Chair Professor Kenneth Raymond Professor Ronald Gronsky Fall 2014 Synthesis and Characterization of Metallocorrole Complexes Copyright © 2014 By Heather Louisa Buckley 2 Abstract Synthesis and Characterization of Metallocorrole Complexes By Heather Louisa Buckley Doctor of Philosophy in Chemistry University of California Berkeley Professor John Arnold, Chair Chapter 1: Recent Developments in Out-of-Plane Metallocorrole Chemistry Across the Periodic Table A brief review of recent developments in metallocorrole chemistry, with a focus on species with significant displacement of the metal from the N4 plane of the corrole ring. Comparisons based on X-ray crystallographic data are made between a range of heavier transition metal, lanthanide, actinide, and main group metallocorrole species. Chapter 2: Synthesis of Lithium Corrole and its Use as a Reagent for the Preparation of Cyclopentadienyl Zirconium and Titanium Corrole Complexes The unprecedented lithium corrole complex (Mes2(p-OMePh)corrole)Li3·6THF (2- 1·6THF), prepared via deprotonation of the free-base corrole with lithium amide, acts as precursor for the preparation of cyclopentadienyl zirconium(IV) corrole (2-2) and pentamethylcyclopentadienyl titanium(IV) corrole (2-3).
    [Show full text]
  • Selectivity of Cobalt Corrole for CO Vs. O2 and N2 in Indoor Pollution Xia Sheng1, Hailiang Zhao1,2 & Lin Du 2
    www.nature.com/scientificreports OPEN Selectivity of Cobalt Corrole for CO vs. O2 and N2 in Indoor Pollution Xia Sheng1, Hailiang Zhao1,2 & Lin Du 2 Coal combustion causes indoor pollution of CO. In this work, DFT calculations on cobalt corrole Received: 4 September 2017 (Co(Cor)) with three most common indoor gas molecules (N2, O2 and CO) were performed. The Mulliken Accepted: 23 October 2017 spin densities show that the ground states of Co(N2)(Cor), Co(CO)(Cor) and Co(OC)(Cor) have an anti- 2 Published: xx xx xxxx ferromagnetic coupling fashion of the electrons on the Co 3dz orbital and the π orbital of the corrole ring. However, Co(O2)(Cor) has a triplet ground state. With the spin contamination corrections, the −1 Co(N2)(Cor) binding energy was obtained at −50.6 kcal mol (B3LYP-D3). While CO can interact with Co(Cor) in two diferent ways, and their binding energies were −22.8 and −10.9 kcal mol−1 (B3LYP-D3) for Co(CO)(Cor) and Co(OC)(Cor), respectively. The natural bond orbital charges on the axial ligands (NO, CO, OC) are increased upon the chemical bond formation. These are the cause of the shorten metal- ligand bond and the increase of the wavenumber of the metal-ligand bond vibrational transitions. While the charges for O2 are decreased, leading to bond elongation as well as the decrease of the wavenumber upon complexation. Overall, O2 was found to be hardly coordinated with Co(Cor). This study provides a detailed molecular understanding of interactions between a gas sensor and gaseous indoor air- pollutants.
    [Show full text]