Process for Producing Fused-Ring Aromatic Compound, and Conjugated Polymer
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Preparation of a Germole-Containing Π-Conjugated Polymer by the Te–Li
Zheng et al. NPG Asia Materials (2020) 12:41 https://doi.org/10.1038/s41427-020-0224-9 NPG Asia Materials ARTICLE Open Access Preparation of a germole-containing π-conjugated polymer by the Te–Li exchange reaction of a tellurophene-containing polymer Feng Zheng1,Sia-ErTan1, Yuki Yanamoto1, Naoki Shida 1, Hiroki Nishiyama1, Shinsuke Inagi1 and Ikuyoshi Tomita 1 Abstract The synthesis and optoelectronic functions of a germole-containing π-conjugated polymer prepared by the reaction of a lithiated polymer precursor are described. A regioregular organometallic polymer having 1,4-dilithio-1,3-butadiene and 9,9-dioctylfluorene-2,7-diyl units was generated by the reaction of a tellurophene-containing polymer having a number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) of 5900 and 1.9, respectively, with n-butyllithium (2.4 equiv) at −78 to −60 °C for 3 h. The prepared lithiated polymer was reacted with dimethylgermanium dichloride (1.5 equiv) at −60 °C to ambient temperature for 12 h in tetrahydrofuran to produce a π-conjugated polymer possessing 1,1-dimethylgermole-2,5-diyl units in 76% yield (Mn = 4400 and Mw/Mn = 1.7). The absorption maximum and onset of the obtained polymer were observed at 465 and 535 nm, respectively, in the UV-vis spectrum, from which the optical band gap of the polymer was estimated to be 2.31 eV. In the photoluminescence spectrum, the obtained polymer exhibits green fluorescence with an emission maximum of 547 nm and a quantum yield of 0.04. The chemical interaction of the dimethylgermole-containing π-conjugated polymer with fluoride was also examined in terms of the changes observed in the UV-vis absorption spectra. -
Environmentsensitive Fluorescent Probe: a Benzophosphole Oxide with an Electrondonating Substituent
Angewandte Chemie International Edition:DOI:10.1002/anie.201500229 Phosphorus Heterocycles German Edition:DOI:10.1002/ange.201500229 Environment-SensitiveFluorescent Probe:ABenzophosphole Oxide with an Electron-Donating Substituent** Eriko Yamaguchi, Chenguang Wang,Aiko Fukazawa,* Masayasu Taki, Yoshikatsu Sato, Taeko Sasaki, Minako Ueda, Narie Sasaki, Tetsuya Higashiyama,* and Shigehiro Yamaguchi* Abstract: Electron-donating aryl groups were attached to phosphine oxide and sulfide derivatives exhibit desirably high electron-accepting benzophosphole skeletons.Among several thermal and chemical stability.Taking advantage of these derivatives thus prepared, one benzophosphole oxide was features,phosphole-based materials have been widely applied particularly interesting,asitretained high fluorescence quan- in organic electronics,[1g,h] including organic light-emitting tum yields even in polar and protic solvents.This phosphole- diodes[3,4] and photovoltaics.[5] However,biological applica- based compound exhibited adrastic color change of its tions have not yet been explored exhaustively.Inthis context, fluorescence spectrum as afunction of the solvent polarity, we would like to disclose here the successful development of while the absorption spectra remained virtually unchanged. highly fluorescent phosphole derivatives,and demonstrate Capitalizing on these features,this phosphole-based compound their potential as fluorescent bioimaging probes. was used to stain adipocytes,inwhich the polarity of Thecombination of an electron-accepting p-skeleton -
Synthesis and Characterization of Bis[1]Benzothieno[3,2-B:20,30-D]Pyrroles: Quantitative Effects of Benzannulation on Dithieno[3,2-B:20,30-D]Pyrroles
molecules Article Synthesis and Characterization of Bis[1]benzothieno[3,2-b:20,30-d]pyrroles: Quantitative Effects of Benzannulation on Dithieno[3,2-b:20,30-d]pyrroles Rylan M. W. Wolfe , Evan W. Culver and Seth C. Rasmussen * Department of Chemistry and Biochemistry, North Dakota State University, NDSU Dept. 2735, P.O. Box 6050, Fargo, ND 58108-6050, USA; [email protected] (R.M.W.W.); [email protected] (E.W.C.) * Correspondence: [email protected]; Tel.: +1-701-231-8747 Received: 14 August 2018; Accepted: 3 September 2018; Published: 6 September 2018 Abstract: The synthesis of four N-functionalized bis[1]benzothieno[3,2-b:20,30-d]pyrroles (BBTPs) is reported in order to provide a more detailed characterization of these fused-ring units, as well as increase the scope of known BBTP units available for application to conjugated materials. The optical, electronic, and structural properties of the resulting BBTP units have been compared to the parent N-alkyl- and N-aryl-dithieno[3,2-b:20,30-d]pyrroles (DTPs), as well as their corresponding 2,6-diphenyl derivatives, in order to fully quantify the relative electronic effects resulting from benzannulation of the parent DTP building block. Such comparative analysis reveals that benzannulation results in a red-shifted absorbance, but to a lesser extent than simple phenyl-capping of the DTP. More surprising is that benzannulation results in stabilization of the BBTP HOMO, compared to the destabilization normally observed with extending the conjugation length of the backbone. Keywords: fused-ring thiophenes; heteroacenes; dithieno[3,2-b:20,30-d]pyrroles; benzannulation; structure-function relationships 1. -
Synthesis and Applications in Fluorescence Imaging
Phosphole P Oxide Containing π Electron Materials: Synthesis and ─ Applications─ in Fluorescence─ Imaging Shigehiro Yamaguchi, 1,2* Aiko Fukazawa, 2 and Masayasu Taki 1 1* Institute of Transformative Bio ─ Molecules (WPI ─ ITbM), Nagoya University 2* Furo, Chikusa, Nagoya 464 ─ 8602, Japan Department of Chemistry, Graduate School of Science, and Integrated Research Consortium on Chemical Sciences (IRCCS), Nagoya University Furo, Chikusa, Nagoya 464 ─ 8602, Japan (Received September 8, 2017; E ─ mail: [email protected]) Abstract: Phosphole P ─ oxide is a useful building block for π ─ conjugated materials due to its nonaromatic and electron ─ accepting character. We have synthesized a series of ring ─ fused derivatives of phosphole P ─ oxide based on the intramolecular nucleophilic cyclization of appropriate alkyne precursors or radical phosphany- lations. Some of the thus obtained compounds exhibited intriguing uorescence properties and were applied to uorescence imaging. A donor ─ acceptor ─ type benzo[b]phosphole P ─ oxide with a (diphenylamino)phenyl group exhibited large solvatochromism in its uorescence spectra, and could hence be used as a staining agent for lipid droplets. C ─ Naphox and PB430, which consist of fully ring ─ fused π ─ conjugated ladder ─ type scaf- folds, exhibited outstanding photostability and their absorption and emission properties were suitable for super ─ resolution STED imaging. Moreover, using PB430 ─ conjugated antibodies, we carried out a 3 ─ D recon- struction of the STED images and developed -
United States Patent (19) 11 Patent Number: 5,936,127 Zhang (45) Date of Patent: Aug
USOO5936127A United States Patent (19) 11 Patent Number: 5,936,127 Zhang (45) Date of Patent: Aug. 10, 1999 54 ASYMMETRIC SYNTHESIS AND CATALYSIS Jacobsen, E.N., “Asymmetric Catalytic Epoxidation of WITH CHIRAL, HETEROCYCLIC Unfunctionalized Olefins,” Catalytic Asymmetric Synthesis, COMPOUNDS Chapter 4.2, 159-202 (1993). Smith, M.B., “Retrosynthesis, Stereochemistry and Confor 75 Inventor: Xumu Zhang, State College, Pa. mations,” Organic Synthesis, Chapter 1.4.C., 58-63 (1994). Trost, B.M. & Li, C.-J., “Novel Umpolung in C-C Bond 73 Assignee: The Penn State Research Foundation, Formation Catalyzed by Triphenylphosphine,” J. AM. University Park, Pa. Chem. Soc., 116, 31.67-3168 (1994). Zhang, C. & Lu, X., “Phosphine-Catalyzed Cycloaddition 21 Appl. No.: 09/006,178 of 2,3-Butadienoates or 2-Butynoates with Electron-Defi cient Olefins. A Novel 3+2 Annulation Approach to Cyclo 22 Filed: Jan. 13, 1998 pentenes,” J. Org. Chem. 60,2906–2908 (1995). Aggarwal, V.K. et al., “A Novel Catalytic Cycle for the Related U.S. Application Data Synthesis of Epoxides Using Sulfure Ylides,” Chem. Eur: 60 Provisional application No. 60/035,187, Jan. 13, 1997, and Journal, 1024–1030 (1996). provisional application No. 60/046,117, May 9, 1997. Aggarwal, V.K., et al., “Direct Asymmetric Epoxidation of Aldehydes Using Catalytic Amounts of Enantiomerically 51 Int. Cl. ........................... C07F 9/02; CO7D 333/50; Pure Sulfides,” J. Am. Chem. Soc., 118, 7004-7005 (1996). CO7D 209/56; B01J 31/00 Basavaiah, D, et al., “The Baylis-Hillman Reaction: A 52 U.S. Cl. ................................. 568/12; 549/41; 549/43; Novel Carbon-Carbon bond Forming Reaction.” Tetrahe 548/418; 548/427: 548/452; 502/162; 502/168 dron, 52,8001-8062 (1996). -
Program 1..154
The 97th Annual Meeting of CSJ Program Chair: INOUE, Haruo(15:30~15:55) Room S1 1S1- 15 Medium and Long-Term Program Lecture Artificial Photosynthesis of Ammonia(RIES, Hokkaido Univ.)○MISAWA, Hiroaki (15:30~15:55) Fourth Building, Section B J11 Chair: INOUE, Haruo(15:55~16:20) 1S1- 16 Medium and Long-Term Program Lecture Mechanism of water-splitting by photosystem II using the energy of visible light(Grad. Sustainable and Functional Redox Chemistry Sch. Nat. Sci. Technol., Okayama Univ.)○SHEN, Jian-ren(15:55~ ) Thursday, March 16, AM 16:20 (9:30 ~9:35 ) Chair: TAMIAKI, Hitoshi(16:20~16:45) 1S1- 01 Special Program Lecture Opening Remarks(Sch. Mater. & 1S1- 17 Medium and Long-Term Program Lecture Excited State Chem. Tech., Tokyo Tech.)○INAGI, Shinsuke(09:30~09:35) Molecular Dynamics of Natural and Artificial Photosynthesis(Sch. Sci. Tech., Kwansei Gakuin Univ.)○HASHIMOTO, Hideki(16:20~16:45) Chair: ATOBE, Mahito(9:35 ~10:50) 1S1- 02 Special Program Lecture Polymer Redox Chemistry toward Chair: ISHITANI, Osamu(16:45~17:10) Functional Materials(Sch. Mater. & Chem. Tech., Tokyo Tech.)○INAGI, 1S1- 18 Medium and Long-Term Program Lecture Recent pro- Shinsuke(09:35~09:50) gress on artificial photosynthesis system based on semiconductor photocata- 1S1- 03 Special Program Lecture Organic Redox Chemistry Enables lysts(Grad. Sch. Eng., Kyoto Univ.)○ABE, Ryu(16:45~17:10) Automated Solution-Phase Synthesis of Oligosaccharides(Grad. Sch. Eng., Tottori Univ.)○NOKAMI, Toshiki(09:50~10:10) (17:10~17:20) 1S1- 04 Special Program Lecture Redox Regulation of Functional 1S1- 19 Medium and Long-Term Program Lecture Closing re- Dyes and Their Applications to Optoelectronic Devices(Fac. -
DK-Value) Dielectric Constant Value DK-Value
Ingeniously simple and reliable level measurement for industry Dielectric values (DK-Value) Dielectric constant value DK-value Substance DK Substance DK A Argon 1,5 Acetal 3,8 Arsine 2,1 Acetaldehyde 15,0 Arsole 2,3 Acetamide 59,2 Asbestos 10,0 Acetic acid 6,2 Ascorbic acid (vitamin C) 2,1 Acetoacetic acid ethyl ester 15,0 Azelaic acid diethylester 5,0 Acetone 21,5 Azoxybenzene 5,2 Acetophenone 18,0 B Acetyl bromide 16,2 Basalt 2,5 Acetyl chloride 15,9 Bauxite 2,5 Acetylacetone 23,0 Beer brew 25,0 Acetylene dibromide 7,2 Beets cuttings 7,3 Acetylene tetrabromide 5,6 Beets seeds 3,5 Aconite acid ester 6,3 Bentonite 8,1 Activated carbon 12,0 Benzal chloride 6,9 Adipic Acid 1,8 Benzaldehyd 17,6 Aerosile 1,0 Benzene 2,3 Aether 4,0 Benzene, heavy 3,2 Allyl alcohol 20,6 Benzil (80°C) 10,0 Allyl chloride 8,2 Benzine 2,0 Allyl iodide 6,1 Benzyl alcohol 13,5 Alum 4,2 Benzyl chloride 7,0 Aluminium bromide 3,4 Benzylamine 4,6 Aluminium foil 10,8 Bitumen 2,8 Aluminium hydroxide 2,5 Black liquor 32,0 Aluminium splinters 7,3 Bone fat 2,7 Aluminium sulfate 2,6 Bonemeal 1,7 Ammonia 15,0 Bore oil emulsion 25,0 Ammonia salt 4,3 Bornylacetat 4,6 Ammonia solution (25%) 31,6 Bromine 3,1 Amyl amine 4,5 Butanoic acid 3,0 Aniline 7,0 C Animal feed grist 2,4 Cacao beans 1,8 Anisealdehyde 22,3 Calcium fluoride 2,5 Anisole 4,5 Camphene 2,3 Anthracite/hard coal 3,2 Caproic acid 2,6 Antimony hydride 1,8 Caprylic acid 2,5 Disclaimer: We assume no liability for the accuracy of the content or for printing errors Page 1 Dielectric constant value DK-value Substance DK -
Aromaticity and Conformational Flexibility of Five-Membered
Struct Chem (2016) 27:101–109 DOI 10.1007/s11224-015-0707-4 ORIGINAL RESEARCH Aromaticity and conformational flexibility of five-membered monoheterocycles: pyrrole-like and thiophene-like structures 1 1,2 3 4,5 Irina V. Omelchenko • Oleg V. Shishkin • Leonid Gorb • Jerzy Leszczynski Received: 13 November 2015 / Accepted: 18 November 2015 / Published online: 7 December 2015 Ó Springer Science+Business Media New York 2015 Abstract Aromaticity and conformational flexibility of Keywords Aromaticity Á Five-membered heterocycles Á the series of five-membered monoheterocycles with group Aromaticity indices Á Aromatic ring flexibility 14–16 heteroatoms, having one or two lone pairs, were studied with ab initio methods using NICS, ASE and I5 indices. For non-planar molecules like phosphole, aro- Introduction maticity of their planar transition states was also studied, and a special modification of ASE index was proposed to Five-membered aromatic heterocycles have been widely that end. It was found that the presence of two lone pairs is investigated because of their importance for biochemistry, generally preferable for aromaticity of all heterocycles medicine, technology and other aspects of life and industry except CPD and silolyl dianions. Heterocycles with group [1]. Aromaticity is a central concept in the chemistry of 16 heteroatoms have consistently lower aromaticity com- heterocycles; it is the main ground for classification and for pared to other groups. A lot of structures should be clas- rationalization of their properties and reactivity [2, 3]. Most sified as moderate aromatic and non-aromatic. Energies of of the popular quantitative indices of aromaticity were out-of-plane deformation do not correlate with other indi- developed and tested on the basis of both six- and five- ces studied, but reveal the same qualitative trends. -
Journal Name COMMUNICATION Peaks Were Also Measured from Pristine Films, with Electron Variation in Device Performance
Please do not adjust margins Journal Name COMMUNICATION Dithieno[3,2-b:2’,3’-d]arsole-containing conjugated polymers in organic photovoltaic devices a,† a a a a Received 00th January 20xx, Joshua P. Green, Hyojung Cha, Munazza Shahid, Adam Creamer, James R. Durrant, and Accepted 00th January 20xx Martin J. Heeney*,a DOI: 10.1039/x0xx00000x www.rsc.org/ Arsole-derived conjugated polymers are a relatively new class of including a high degree of optoelectronic tunability via the materials in the field of organic electronics. Herein, we report the alteration of the exocyclic groups.22–25 For example, Park et al. synthesis of two new donor polymers containing fused have reported a promising donor co-polymer of a DTP-oxide dithieno[3,2-b:2’,3’-d]arsole units and report their application in and a dithienyl-benzo[1,2-b:4,5-b’]dithiophene (BDT) which bulk heterojunction solar cells for the first time. Devices based exhibited power conversion efficiencies (PCEs) of up to 6.10% in 26 upon blends with PC71BM display high open circuit voltages around blends with phenyl-C61-butyric acid methyl ester (PCBM). 0.9V and demonstrate power conversion efficiencies around 4%. However, the vast majority of work relating to DTP units has focused on those containing pentavalent phosphorus atoms, Research into new conjugated polymers for use in organic and there has been little exploration of the properties of DTPs electronics applications such as organic photovoltaics (OPVs), containing trivalent phosphorus. This is likely due to the oxygen- organic field effect transistors (OFETs), and organic light sensitivity of organophosphorus atoms in the +3 oxidation emitting diodes (OLEDs) has often focussed on the use of state, which can lead to rapid and or uncontrolled oxidation of heavier atoms as replacements for common elements such as materials under atmospheric conditions. -
Structure and Reactivity Studies of Simple Phospholes
Lakehead University Knowledge Commons,http://knowledgecommons.lakeheadu.ca Electronic Theses and Dissertations Retrospective theses 1977 Structure and reactivity studies of simple phospholes Kleemola, Daniel http://knowledgecommons.lakeheadu.ca/handle/2453/2283 Downloaded from Lakehead University, KnowledgeCommons STRUCTURE AND REACTIVITY STUDIES OF SIMPLE PHOSPHOLES BY DANIEL KLEEMOLA A THESIS SUBMITTED TO THE DEPARTMENT OF CHEMISTRY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE Lakehead University Thunder Bay, Ontario, Canada September, 1977 ProQuest Number: 10611602 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. Pro ProQuest 10611602 Published by ProQuest LLC (2017). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346 /■f77 Copyright © Daniel Kleemola 1977 ^Canadian Thesi s on Microfiche No. 34734 253321 i ABSTRACT Newer techniques of phosphole synthesis, particularly those which lead to simple phospholes substituted with active functional groups, are briefly surveyed. A detailed account of chemical, physico-chemical, spectroscopic and theoretical studies related to the phosphole aromaticity problem is given and the present conflicting position is discussed. Dielectric relaxation measurements, based on the reorientation of a dipole in an alternating electromagnetic field, were obtained for seven phospholes and phosphole derivatives in an attempt to determine phosphole pyramidal inversion barriers. -
Synthesis, Structural Characterization, and Optical Properties of Benzene-Fused Tetracyclic and Pentacyclic Stiboles
molecules Communication Synthesis, Structural Characterization, and Optical Properties of Benzene-Fused Tetracyclic and Pentacyclic Stiboles Mio Matsumura 1, Yuki Matsuhashi 1, Masato Kawakubo 1, Tadashi Hyodo 2, Yuki Murata 1 , Masatoshi Kawahata 2,†, Kentaro Yamaguchi 2 and Shuji Yasuike 1,* 1 School of Pharmaceutical Sciences, Aichi Gakuin University, 1-100 Kusumoto-cho, Chikusa-ku, Nagoya 464-8650, Japan; [email protected] (M.M.); yuki325fi[email protected] (Y.M.); [email protected] (M.K.); [email protected] (Y.M.) 2 Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan; [email protected] (T.H.); [email protected] (M.K.); [email protected] (K.Y.) * Correspondence: [email protected]; Tel.: +81-52-757-6774 † Present Address: Showa Pharmaceutical University, 3-3165 Higashi-Tamagawagakuen, Machida, Tokyo 194-8543, Japan. Abstract: The expectation that antimony (Sb) compounds should display phosphorescence emissions based on the “heavy element effect” prompted our interest in the introduction of antimony to a biaryl as the bridging atom in a fused heterole system. Herein, the synthesis, molecular structures, and optical properties of novel benzene-fused heteroacenes containing antimony or arsenic atoms are described. The stiboles and arsole were prepared by the condensation of dibromo(phenyl)stibane or dichloro(phenyl)arsine with dilithium intermediates derived from the corresponding dibromo Citation: Matsumura, M.; compounds. Nuclear magnetic resonance (NMR) spectroscopy and X-ray crystal analysis revealed Matsuhashi, Y.; Kawakubo, M.; that the linear pentacyclic stibole was highly symmetric in both the solution and crystal states. -
Emissive Organic Radicals Substituted by Phosphorus
EMISSIVE ORGANIC RADICALS SUBSTITUTED BY PHOSPHORUS- CONTANING MOITIES: APPLICATIONS AS OLED MATERIALS by Ragene Thornton, B.S. A thesis submitted to the Graduate Council of Texas State University in partial fulfillment of the requirements for the degree of Master of Science with a Major in Chemistry August 2019 Committee Members: Todd Hudnall, Chair William Brittain, Co-Chair Benjamin Martin, Co-Chair COPYRIGHT by Ragene Thornton 2019 FAIR USE AND AUTHOR’S PERMISSION STATEMENT Fair Use This work is protected by the Copyright Laws of the United States (Public Law 94-553, section 107). Consistent with fair use as defined in the Copyright Laws, brief quotations from this material are allowed with proper acknowledgement. Use of this material for financial gain without the author’s express written permission is not allowed. Duplication Permission As the copyright holder of this work I, Ragene Thornton, authorize duplication of this work, in whole or in part, for educational or scholarly purposes only. ACKNOWLEDGEMENTS To begin, I would like to thank Dr. Hudnall for giving me the opportunity to pursue my passion in his research lab. I would also like to extend this thanks to all the wonderful people in the Hudnall group; I would not have been able to make it through without the care and support from my peers. I have been part of the Hudnall group for two years and throughout my time in the group I have gained friends, wisdom and a family. I would also like to extend a thanks to the Chemistry/Biochemistry faculty and staff. A special thank you to my parents and siblings, for loving and supporting me throughout my academic career.