DOCSLIB.ORG

P-Stereogenic Diamondoid Phosphines

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
P-Stereogenic Diamondoid Phosphines ISSN 2518-1548 (Online) Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71) ISSN 2308-8303 (Print) UDC 547.316+54.057 https://doi.org/10.24959/ophcj.20.199828 E. D. Butova1, V. V. Bahonsky1,2, R. I. Yurchenko1, S. O. Butov1, M. M. Moroz1, A. A. Fokin1 1 National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, Ukraine 37, Peremohy Ave., Kyiv, 03056, Ukraine. E-mail: [email protected] 2 Justus Liebig University Giessen, Germany P-Stereogenic diamondoid phosphines Despite diamondoid phosphines have found many synthetic applications and are even available commer- cially the chemistry of chiral diamondoid phosphines remains largely unexplored. Aim. To develop the convenient preparative method for the preparation of sterically-congested P-stereogenic secondary diamodoidyl phosphines as potential organocatalysts and ligands in the asymmetric synthesis. Results and discussion. A convenient method for the synthesis of P-stereogenic diamondoid phosphines with high yields through the phosphorylation of hydroxydiamondoids in trifluoroacetic acid followed by the re- duction of the corresponding asymmetric chlorophosphonates has been proposed. The secondary phosphines obtained form stable complexes with borane that can be used to separate diamondoid phosphines into enan- tiomers. Experimental part. The experimental procedures for the preparation of 1- and 4-diamantyl-1-adamantyl- and phenylphosphines were developed; the structures of new compounds were confirmed by NMR and HRMS spectral data. Conclusions. A number of P-stereogenic mixed diamondoidylaryl phosphines and the secondary phos- phines containing exclusively diamondoid substituents has been prepared. A degree of steric bulkiness is deter- mined by the combination of diamondoid substituents around a phosphorus atom where 1-diamantyl derivatives are the most sterically-congested. The compounds obtained are potential ligands in asymmetric catalysis. Key words: phosphine borane complexes; 1-adamantyldiamantylphosphine; 4-adamantyldiamantylphosphine; 1-phenyldiamantylphosphine; 4-phenyldiamantylphosphine; P-stereogenic phosphines К. Д. Бутова1, В. В. Бахонський1,2, Р. І. Юрченко1, С. О. Бутов1, М. М. Мороз1, А. А. Фокін1 1 НТУУ «Київський політехнічний інститут імені Ігоря Сікорського», Україна 2 Гіссенський університет імені Юстуса Лібіха, Німеччина Р-стереогенні діамандоїдні фосфіни Незважаючи на те, що діамандоїдні фосфіни широко використовуються в органічному синтезі і навіть доступні комерційно, хімія хіральних діамандоїдних фосфінів залишається не дослідженою. Мета. Розробити зручний препаративний метод синтезу стереоускладнених Р-стереогенних вторин- них діамандоїдних фосфінів, які можуть бути використані як ліганди в асиметричному синтезі, а також як органокаталізатори. Результати та їх обговорення. Запропоновано зручний метод синтезу P-стереогенних діамандоїдних фосфінів шляхом фосфорилювання гідроксипохідних діамандоїдів у трифтороцтовій кислоті з подальшим відновленням відповідних асиметричних хлорофосфонатів з високими виходами. Одержані таким чином фосфіни утворюють стійкі комплекси з бораном, які розглядаються як проміжні сполуки для подальшого розділення енантіомерів. Експериментальна частина. Був розроблений препаративний метод синтезу 1- і 4-діамантил-, 1-ада- мантил- і фенілфосфінів, структури яких підтверджено мас-спектрометричними і ЯМР-спектральними да- ними. Висновки. Одержано ряд Р-стереогенних змішаних діамандоїларилфосфінів та вторинних фосфінів, які містять виключно діамандоїдні замісники. Ступінь стеричного навантаження сполук визначається ком- бінацією діамандоїдних замісників навколо атома фосфору, де похідні 1-діамантилу найбільш стерично ускладнені. Одержані сполуки є потенційними лігандами в асиметричному каталізі. Ключові слова: боранові комплекси фосфінів; 1-адамантилдіамантилфосфін; 4-адамантилдіамантилфосфін; 1-фенілдіамантилфосфін; 4-фенілдіамантилфосфін; Р-стереогенні фосфіни Copyright © 2020, E. D. Butova, V. V. Bahonsky, R. I. Yurchenko, S. O. Butov, M. M. Moroz, A. A. Fokin This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0) Organophosphorus compounds are among useful rectly on the phosphorus” [1]. Accordingly, over the last ligands in catalysts where further progress is largely decades many chiral tertiary phosphines trademar- associated with P-stereogenic phosphines as stated ked as Quinox-P, Benz-P, Pincer-P, and some by W. Knowles in his Nobel Lecture: “…if one wanted others [2] become available commercially. These li- to get high values, the asymmetry would have to be di- gands allow obtaining high yields and enantiomeric 35 ISSN 2308-8303 (Print) Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71) ISSN 2518-1548 (Online) phines containing phenyl, adamantyl, and diamantyl 1. HNO 3 OH + groups. The key starting compounds – 1-hydroxydia- 2. H SO , H O 2 4 2 mantane 2a and 4-hydroxydiamantane 2b were pre- 3. Chromatographic separation pared from diamantane 1 through the nitroxylation OH with the concentrated nitric acid and further acidic 1 2a 2b hydrolysis as previously described [16] (Scheme 1). Scheme 1. The synthesis of 1- and 4-hydroxydiamantanes 2a,b were converted to the cor- responding chlorophosphonates 3ad, 3bd, 3ac, and excesses of products in various transformations in- 3bcHydroxydiamantanes volving hydroacylations [3, 4], catalytic asymmetric roacetic acid [17, 18] utilizing PhPCl2 and AdPCl2 as hydrogenations [5, 6] and many others [7]. phosphorylatingthrough the phosphorylationagents (Scheme 2). reaction Chlorophospho in trifluo-- Achiral bulky diadamantyl alkyl phosphines have been nates 3ad, 3bd, 3ac, and 3bc were further reduced introduced as effective ligands where Ad2P(nBu) and 4 in tetrahydrofuran to give phosphines 4ad, Ad2PBn are now commercially available as cataCXiumA 4bd, 4ac, and 4bc. Stability towards oxygen is an im- and cataCXiumABn, respectively. The palladium complex portantwith LiAlH factor that determines the practical poten- with Ad2P(n tial of phosphine ligands. In contrast to the primary catalyst in Suzuki reactions for aryl chlorides [8], in diamondoid phosphines that were reactive towards Bu) as a ligand acts as a highly efficient oxygen, the secondary diamondoid phosphines even coupling [10] and for the arylations of ketones [11]. with one diamantyl group (4ac and 4bc) were quite Thethe arylationNa2PdCl4/Ad reactions2PBn system [9], in has Buchwald−Hartwig been successfully persistent towards oxidation. Nevertheless, for puri- applied for the Sonogashira coupling [12]. Extremely via column chromatography phosphines 4ad, bulky Ad3P in the presence of palladium acetate was 4bd, 4ac, and 4bc were converted into boron comp- recently used as a catalyst for the arylation of unsa- lexesfications 5ad, 5bd, 5ac, and 5bc 3 turated cyclic ketoethers [13]. The chemistry of chiral The structures of the phosphines obtained we- diamondoid phosphines still remains almost unex- re proven by a number of spectral in the BH characteristics./THF system. plored. Only recently the rhodium complex of di-1-ada- The 13C NMR DEPT 135 spectrum of 4-diamantyl- mantylphosphino-(tert-butylmethylphosphino)me- 1-adamantylphosphine borane 5bd contained four thane (BulkyP*) was prepared and tested as a ligand 2 for Rh-promoted asymmetric hydrogenations of the axial symmetry of diamondoid fragments. In cont- functionalized alkenes where effective transforma- rast,CH , fourthe 13 CH,C NMR and spectrum two C resonances. of 5ad contained It agrees ten with re- tions were achieved under very low catalyst loadings sonances of the prochiral 1-diamantyl moiety due to the presence of the chiral P-center in the structure. All above makes important the preparation of P-ste- The NMR spectra of complexes 5ac and 5bc displa- reogenic(< 0.001 mol %)diamondoid [14]. phosphines since the incorpo- yed a dynamic behavior and were measured under ration of bulky substituents into phosphine may en- cooling. hance the catalytic activity and selectivity of the ca- The borane protecting group can further be remo- talyst. Previously, we prepared a number of P-stereo- ved either by the treatment with excess of diethyl- genic mixed diamondoidylaryl phosphines [15]. In this amine [19] or, more conveniently, using pyrrolidine paper we present the preparation of the secondary [20] under mild reaction conditions that retain the ab- diamondoid phosphines with the potential as ligands P-stereogenic center. in asymmetric catalysis. Experimental part solute configuration of the Results and discussion NMR spectra were recorded on a Bruker Avance III The aim of this work was to develop a prepara- 1 - tive method for the synthesis of chiral bulky phos- quencies for 13C and 31 spectrometer at 400 and 600 MHz (for H, the fre O H H P NMR are specifiedBH3 below) OH 1 P Cl P 1 P 1 R PCl2 1 LiAlH4 R BH3/THF R R F3CCOOH 2a,b 3ad (76%) 4ad (80%) 5ad (96%) 3bd (92%) 4bd (85%) 5bd (95%) 3ac (34%) 4ac (40%) 5ac (95%) 3bc (45%) 4bc (43%) 5bc (95%) a: 1-diamantyl c: R1 = , d: R1 = b: 4-diamantyl Scheme 2. The synthesis of borane complexes of 1- and 4-diamantyl-1-adamantyl phosphines and 1- and 4-diamantylphenyl phosphines 36 ISSN 2518-1548 (Online) Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71) ISSN 2308-8303 (Print) 1 13 31 with TMS ( 3PO4 ( P) as internal J = J = 31 1 J = P{ 3 H and C) and H (C−Р) 1.9 Hz), 43.8 (C, d, (C−Р)24 6034ClOP Hz), 45.7404.2036 (C, d, standards. High-resolution mass spectra (HRMS) were [M(C−Р)+]; found60 Hz).
Load more

Recommended publications
  • Direct Diamondoid-To-Diamond Phase Transitions Sulgiye Park1, Jin Liu1, Jeremy E
    Direct diamondoid-to-diamond phase transitions Sulgiye Park1, Jin Liu1, Jeremy E. P. Dahl2, Rodney C. Ewing1, Wendy L. Mao1, Yu Lin2* 1Department of Geological Sciences, Stanford University, Stanford, CA, 94305, USA 2Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA Pressure-temperature-phase space of carbon-hydrogen systems has been a topic of intense investigation due to their importance in a wide range of fields, ranging from planetary sciences to condensed matter physics. Here, we explore how diamondoids, a unique class of hydrogen- terminated carbon nanomaterials, undergo phase and chemical transformations, and dissociate into various carbon forms under static compression and high temperature. Entirely constituted by sp3 bonded carbon atoms superimposed on the cubic diamond lattice and terminated by hydrogen atoms, diamondoid molecules are stiff, dense, and contain exceptional properties of both bulk diamond and small hydrocarbon molecules [1]. This makes diamondoids attractive for a wide range of applications, ranging from polymer synthesis, nanotechnology, drug delivery, drug targeting to molecular electronics. At high pressure and ambient temperature, bulk moduli of diamondoid crystals are dependent on their molecular geometry, wherein a higher dimensionality of a diamondoid molecule (as opposed to the simple packing schemes within the unit cell) yields a lower compressibility [2]. At high pressure and high temperature, all diamondoids studied exhibit direct diamondoid-to-graphite and diamondoid-to-diamond phase transitions. The pressure and temperature needed for the diamondoid-to-diamond conversion is significantly lower than those for graphite [3] and other hydrocarbons (e.g., polycyclic aromatic hydrocarbons [4]). For instance, triamantane transforms into diamond at 15 GPa with a temperature onset of 1200 K.
    [Show full text]
  • Diamondoid Molecules: with Applications in Biomedicine
    b1325 Diamondoid Molecules Chapter 1 of the book on Diamondoid Molecules with Applications in Biomedicine, Materials Science, Nanotechnology & Petroleum Science GA Mansoori, PLB de Araujo and E.S de Araujo (Authors) World Sci Pub Co, Hackensack, NJ, 2012 www.worldscientific.com/worldscibooks/10.1142/7559#t=aboutBook Chapter 1 Molecular Structure and Chemistry of Diamondoids 1.1. Introduction Diamondoid molecules are cage-like, ultra stable and saturated hydrocar-bons. The basic repetitive unit of the diamondoids is a ten- carbon tetracy-clic cage system called “adamantane” (Fig. 1.1). They are called “diamondoid” because they have at least one adamantane unit and their carbon–carbon framework is completely or largely superimposable on the diamond lattice (Balaban and Schleyer, 1978; Mansoori, 2007). The dia-mond lattices structure was first determined in 1913 by Bragg and Bragg using X-ray diffraction analysis (Bragg and Brag, 1913). Diamondoids show unique properties due to their exceptional atomic arrangements. Adamantane consists of cyclohexane rings in “chair” conformation. The name adamantane is derived from the Greek language word for diamond since its chemical structure is like the three- dimensional diamond subunit as it is shown in Fig. 1.2. 1.2. Classification and Crystalline Structure of Diamondoids The first and simplest member of the diamondoids group, adamantane, is a tricyclic saturated hydrocarbon (tricyclo[3.3.1.1(3.7)]decane, according to the von Bayer systematic nomenclature). Adamantane is followed by its 1 b1325_Ch-01.indd 1 7/23/2012 6:17:29 PM b1325 Diamondoid Molecules Diamondoid Molecules www.worldscientific.com/worldscibooks/10.1142/7559#t=aboutBook 2 Fig.
    [Show full text]
  • Inorganic Chemistry for Dummies® Published by John Wiley & Sons, Inc
    Inorganic Chemistry Inorganic Chemistry by Michael L. Matson and Alvin W. Orbaek Inorganic Chemistry For Dummies® Published by John Wiley & Sons, Inc. 111 River St. Hoboken, NJ 07030-5774 www.wiley.com Copyright © 2013 by John Wiley & Sons, Inc., Hoboken, New Jersey Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permis- sion of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 646-8600. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http://www.wiley. com/go/permissions. Trademarks: Wiley, the Wiley logo, For Dummies, the Dummies Man logo, A Reference for the Rest of Us!, The Dummies Way, Dummies Daily, The Fun and Easy Way, Dummies.com, Making Everything Easier, and related trade dress are trademarks or registered trademarks of John Wiley & Sons, Inc. and/or its affiliates in the United States and other countries, and may not be used without written permission. All other trade- marks are the property of their respective owners. John Wiley & Sons, Inc., is not associated with any product or vendor mentioned in this book.
    [Show full text]
  • Hybrid Metal–Organic Chalcogenide Nanowires with Electrically Conductive Inorganic Core Through Diamondoid-Directed Assembly Hao Yan1,2†, J
    Lawrence Berkeley National Laboratory Recent Work Title Hybrid metal-organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly. Permalink https://escholarship.org/uc/item/1xt3j30k Journal Nature materials, 16(3) ISSN 1476-1122 Authors Yan, Hao Hohman, J Nathan Li, Fei Hua et al. Publication Date 2017-03-01 DOI 10.1038/nmat4823 Peer reviewed eScholarship.org Powered by the California Digital Library University of California ARTICLES PUBLISHED ONLINE: 26 DECEMBER 2016 | DOI: 10.1038/NMAT4823 Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly Hao Yan1,2†, J. Nathan Hohman3†, Fei Hua Li1,2†, Chunjing Jia1, Diego Solis-Ibarra4, Bin Wu1,2, Jeremy E. P. Dahl1, Robert M. K. Carlson1, Boryslav A. Tkachenko5, Andrey A. Fokin5, Peter R. Schreiner5, Arturas Vailionis6, Taeho Roy Kim1,2, Thomas P. Devereaux1, Zhi-Xun Shen1 and Nicholas A. Melosh1,2* Controlling inorganic structure and dimensionality through structure-directing agents is a versatile approach for new materials synthesis that has been used extensively for metal–organic frameworks and coordination polymers. However, the lack of ‘solid’ inorganic cores requires charge transport through single-atom chains and/or organic groups, limiting their electronic properties. Here, we report that strongly interacting diamondoid structure-directing agents guide the growth of hybrid metal–organic chalcogenide nanowires with solid inorganic cores having three-atom cross-sections, representing the smallest possible nanowires. The strong van der Waals attraction between diamondoids overcomes steric repulsion leading to a cis configuration at the active growth front, enabling face-on addition of precursors for nanowire elongation. These nanowires have band-like electronic properties, low eective carrier masses and three orders-of-magnitude conductivity modulation by hole doping.
    [Show full text]
  • Reappraisal of Hydrocarbon Biomarkers in Archean Rocks
    Reappraisal of hydrocarbon biomarkers in Archean rocks Katherine L. Frencha,1,2, Christian Hallmannb,c, Janet M. Hoped, Petra L. Schoone, J. Alex Zumbergee, Yosuke Hoshinof, Carl A. Petersf, Simon C. Georgef, Gordon D. Lovee, Jochen J. Brocksd, Roger Buickg, and Roger E. Summonsh aJoint Program in Chemical Oceanography, Massachusetts Institute of Technology and Woods Hole Oceanographic Institution, Cambridge, MA 02139; bMax Planck Institute for Biogeochemistry, 07745 Jena, Germany; cCenter for Marine Environmental Sciences, University of Bremen, 28359 Bremen, Germany; dResearch School of Earth Sciences, The Australian National University, Canberra, ACT 0200, Australia; eDepartment of Earth Sciences, University of California, Riverside, CA 92521; fDepartment of Earth and Planetary Sciences, Macquarie University, Sydney, NSW 2109, Australia; gDepartment of Earth & Space Sciences and Astrobiology Program, University of Washington, Seattle, WA 98195-1310; and hDepartment of Earth, Atmospheric, and Planetary Sciences, Massachusetts Institute of Technology, Cambridge, MA 02139 Edited by Andrew H. Knoll, Harvard University, Cambridge, MA, and approved March 16, 2015 (received for review October 21, 2014) Hopanes and steranes found in Archean rocks have been pre- hydrocarbon biomarkers hosted in Archean rocks would either sented as key evidence supporting the early rise of oxygenic recast or solidify the late Archean framework in which we un- photosynthesis and eukaryotes, but the syngeneity of these derstand one of the most profound biologically mediated trans- hydrocarbon biomarkers is controversial. To resolve this debate, formations of the planet—the Great Oxidation Event [GOE; ∼2.4 we performed a multilaboratory study of new cores from the billion years ago (Ga)] (13). Pilbara Craton, Australia, that were drilled and sampled using unprecedented hydrocarbon-clean protocols.
    [Show full text]
  • Studies Towards the Synthesis of Nano-Diamondoid Hydrocarbon Cyclohexamantane
    Studies Towards the Synthesis of Nano-Diamondoid Hydrocarbon Cyclohexamantane A thesis submitted by Tao Qu in partial fulfilment of the requirements for the degree of Doctor of Philosophy Department of Chemistry Imperial College London South Kensington London, SW7 2AZ United Kingdom September 2007 Abstract Adamantane (C 10 H16 ) is the smallest unit cage structure of the diamond crystal lattice. Other diamondoid hydrocarbons are also known, such as diamantane and triamantane. In 2003, the isolation and structural elucidation of a highly symmetrical and remarkably 1 stable “natural product” cyclohexamantane (C 26 H30 ) was reported. The structure of the nanometer-sized hydrocarbon cyclohexamantane was shown by X-ray crystallography to be the largest fully characterized fragment of the diamond lattice. Higher order diamondoid hydrocarbons may have great potential applications in pharmaceuticals, microelectronics and nanotechnology. 2 Prior to von Schleyer’s outstanding synthesis 3, adamantane was a rare compound and only available in small quantities. The success to von Schleyer’s synthesis was his appreciation of the fact that adamantane is the most stable hydrocarbon of formula C10 H16 . He used this knowledge to bring about the Lewis acid catalysed rearrangement (via a sequence of Wagner-Meerwein shifts) of a strained hydrogenated cyclopentadiene dimer (C 10 H16 ) to provide adamantane in high yield. Our research goal is to prepare hydrocarbon precursors of formula C26 H32 and to study their dehydrogenative rearrangements under acidic conditions as a concise synthetic route to cyclohexamantane (C26 H30 ). Our investigations into two different approaches to build the rearrangement precursors (C 26 H32 ) are described in this thesis. In the first approach, a four-directional synthesis of the rearrangement precursor has been examined through Route A and Route B .
    [Show full text]
  • (12) United States Patent (10) Patent No.: US 8,716,539 B2 Schreiner Et Al
    US008716539B2 (12) United States Patent (10) Patent No.: US 8,716,539 B2 Schreiner et al. (45) Date of Patent: May 6, 2014 (54) METHOD FOR PRODUCING SUBSTITUTED Y. Klimochkin et al., “Synthesis and hydrolytic conversions of DAMANTANES nitroxy derivatives of homoadamantane, protoadamantane and bicycle3.3.1 nonane', Russian Journal of Organic Chemistry, (75) Inventors: Peter R. Schreiner, Wettenberg (DE): (1993), 29(7), 1358-1364. Andrey A. Fokin, Giessen (DE) T. Courtney et al., “The Chemistry of Diamantane. Part 1. Synthesis and Some Functionalisation Reactions” (1972).J.C.S Perkin I. 2691 (73) Assignee: Justus-Liebig-Universitaet Giessen, 2696. Giessen (DE) T. Gund et al., “Diamantane.II. Preparation of Derivatives of Diamantane” (1974).J. Org Chem., vol. 39(20), 2987-2994. (*) Notice: Subject to any disclaimer, the term of this L. Vodicka et al., “Synthesis of Diamantanedicarboxylic Acids with patent is extended or adjusted under 35 the Carboxy Groups Bonded at Tertiary Carbon Atoms” (1983) Col U.S.C. 154(b) by 704 days. lection Czechoslovak Chem. Commun., vol. 48, 1162-1172. G. Olah et al., "Nitration of Adamantane and Diamantane with (21) Appl. No.: 12/086,058 Nitronium Tetrafluoroborate” (1993).J. American Chemical Soc. , 115,7246-7249. (22) PCT Filed: Dec. 4, 2006 F. Blaney et al., “Diamondoid Rearrangements in Chlorosulphonic Acid. A Highly Regioselective Route to Apically Disubstituted (86). PCT No.: PCT/DE2OO6/OO2146 Diamantanes' (1975) Tetrahadron Letters, No. 2, 99-100. A. Fokinet al., “Functionalized Nanodiamonds Part I. An Experi S371 (c)(1), mental Assessment of Diamantane and Computational Predictions (2), (4) Date: Oct. 29, 2009 for Higher Diamondoids” (2005) Chem.
    [Show full text]
  • Carbon Nanothreads from Compressed Benzene 20 May 2015
    Carbon nanothreads from compressed benzene 20 May 2015 Carbon nanomaterials such as fullerenes, nanotubes, and graphene have outstanding physical properties associated with their low dimensionality and graphite-like chemical bonding. The breakthrough discovery is the synthesis of one- dimensional, carbon nanothreads with diamond-like bonding only 0.6 nanometers in diameter. Computational modeling suggests that these nanothreads could be stronger than carbon nanotubes or conventional high-strength polymers and also extremely stiff. They are synthesized in macroscopic quantities by slow decompression of benzene frozen at high Rendering of carbon nanothreads as suggested by pressures and brought to ambient conditions. In characterization techniques. Brown spheres, carbon; contrast to the high-temperature, gas-phase blue spheres, hydrogen. The rendering is superimposed synthesis used for conventional nanotubes, kinetic on a transmission electron microscopy image of the carbon nanothreads. The image shows striations at a chemical control such as is employed in organic separation of 6.4 Å, extending for tens of nanometers. chemistry is used for the synthesis of the This model is consistent with x-ray and neutron nanothreads. It may be possible to synthesize a scattering data as well as computational simulations. whole family of diamondoid nanothread materials, Credit: Professor J.V. Badding even with crosslinking between threads, or with added chemical functionality, by this chemical approach, which is potentially more versatile than difficult-to-control gas-phase approaches. A new carbon nanomaterial – the thinnest possible one-dimensional thread that still retains a diamond- Using fabrication techniques developed based on like structure – was created by the controlled, slow this breakthrough, it might be possible to produce compression and decompression of benzene.
    [Show full text]
  • The Chemistry of Multi-Component and Hierarchical Framework Compounds
    Chemical Society Reviews The Chemistry of Multi-component and Hierarchical Framework Compounds Journal: Chemical Society Reviews Manuscript ID CS-SYN-04-2019-000250.R2 Article Type: Review Article Date Submitted by the 17-Jun-2019 Author: Complete List of Authors: Feng, Liang; Texas A&M University College Station, Chemistry Wang, Kunyu; Texas A&M University, Chemistry Day, Gregory S; Department of Chemistry, Texas A&M Energy Institute, Texas A&M University, College Station, Texas Zhou, Hong-Cai; Texas A&M University, Chemistry Page 1 of 37 PleaseChemical do not Society adjust Reviews margins Journal Name ARTICLE The Chemistry of Multi-component and Hierarchical Framework Compounds Received 00th January 20xx, a a a a, b Accepted 00th January 20xx Liang Feng† , Kun-Yu Wang† , Gregory S. Day , Hong-Cai Zhou* DOI: 10.1039/x0xx00000x Multi-component hierarchically porous materials are an emerging class of materials with tailored compositions, tunable apportionments and sophisticated applications. An increasing demand for multifunctionalities and hierarchical www.rsc.org/ structures has resulted in extensive studies on multi-component hierarchical metal-organic frameworks and other open framework compounds. This review article focuses on recent advances of multi-component hierarchically porous materials, covering the design and synthetic strategies of these architectures, their characterizations, and the latest applications. Multivariate MOFs prepared under various synthetic conditions (one-pot or post-synthetic) and their building block distributions are introduced and summarized. This is followed by a short review of characterization techniques including solid-state NMR and photothermal induced resonance, and their potential applications in gas storage, separation, heterogeneous catalysis, guest delivery, and luminescence.
    [Show full text]
  • Electronic Structure and Optical Properties of Pristine and Modified
    Electronic Structure and Optical Properties of Pristine and Modi¯ed Diamondoids vorgelegt von Diplom-Physiker Lasse Landt Berlin von der FakultÄatII - Mathematik und Naturwissenschaften der Technischen UniversitÄatBerlin zur Erlangung des akademischen Grades Doktor der Naturwissenschaften - Dr. rer. nat. - genehmigte Dissertation Promotionsausschuss: Vorsitzender: Prof. Dr. Mario DÄahne Berichter/Gutachter: Prof. Dr. Thomas MÄoller Berichter/Gutachter: PD Dr. Uwe Hergenhahn Tag der wissenschaftlichen Aussprache: 15. November 2010 Berlin 2010 D 83 ii Abstract In this work the optical properties of diamondoids, a new form of perfectly size- and shape-selected, neutral, and hydrogen-passivated diamond nanocrystals, are investi- gated. The absorption and luminescence properties are studied as a function of size and shape and the optical gap of the investigated diamondoid species has been determined. The shape is found to dominate the optical response of the diamondoid outweighing size e®ects in the investigated size range. According to their growth scheme and their absorption behavior the diamondoids are categorized as 1D, 2D and 3D nanodiamond structures. The tetrahedral C26H32 cluster is identi¯ed as the smallest diamond nanos- tructure to exhibit bulk-like absorption behavior. Further, diamondoids are shown to exhibit photoluminescence in the ultraviolet spectral region. The spectra for eight dia- mondoids of di®erent sizes and shapes have been recorded. The photoluminescence is spectrally broad and only little size-dependent. A spectral structure is observed and a careful analysis allows for a tentative assignment to di®erent vibrational modes. Quan- tum chemical electronic structure calculations and group theoretical consideration have been employed to facilitate the interpretation of the experimental data.
    [Show full text]
  • Benzene-Derived Diamondoid Carbon Nanothreads J
    3,0 Tube Polymer 1 Crespi et.al. H Phys Rev Le* Hoffman et.al. JACS 87 (2001) 133, 9023 (2011) C Benzene-Derived Diamondoid Carbon Nanothreads J. V. Badding, T. Fitzgibbons, V. Crespi, E. Xu, N. Alem Pennsylvania State University G. Cody Carnegie Institution of Washington S. K. Davidowski Arizona State University R. Hoffmann, B. Chen Funding: EFRee DOE Energy Cornell University Frontier Research Center M. Guthrie European Spallation Source Carbon Nanomaterial Dimensionality and Hybridization 0-d 1-d 2-d sp2 C60 nanotubes Graphene sp3 ? diamondoids Graphane sp3 Carbon Nanotube Theory Predictions 3,0 Tube Polymer I Hydrogen First evidence that very small sp3 sp3 tube predicted to form during a carbon nanotubes are high pressure reaction of benzene thermodynamically stable. Stojkovic, D. et.al. PRL 87, (2001) Wen, X-D. et.al. JACS 133, 9023 (2011) Benzene Rapid Decompression: Amorphous Product Liquid Benzene Yellow/white solid Diamond 25 GPa anvil cell Diamond gasket aer Anvil cell decompression Decompression rate ≈12-20 GPa/hr Broad spectral features Powder X-Ray Diffraction UV Raman Spectrum 257 nm excitaon Slow Decompression in Larger Volumes SNAP/ORNL Paris- Edinburgh cell allows for large sample volumes 43 cm (mg to tens of mg scale). Decompression rate ≈ 2-7 GPa/hr PCD WC Steel C13 Solid State NMR Reveals sp3 Bonding sp2 sp3 ~80 % sp3/ tetrahedral bonding 20% 80% TEM of Slowly Decompressed Benzene: Nanothreads! 10 nm After Sonication Fitzgibbons et.al., Benzene-derived carbon nanothreads. Nat. Mater. 14, 43-47 (2015) Crystalline order
    [Show full text]
  • Nanotechnology of Diamondoids for the Fabrication of Nanostructured Systems
    Nanotechnology Reviews 2020; 9: 650–669 Review Ka-Wai Yeung, Yuqing Dong, Ling Chen, Chak-Yin Tang*, Wing-Cheung Law, and Gary Chi-Pong Tsui Nanotechnology of diamondoids for the fabrication of nanostructured systems https://doi.org/10.1515/ntrev-2020-0051 received June 15, 2020; accepted June 22, 2020 1 Introduction Abstract: Diamondoids are cage-like hydrocarbon materials Since the discovery of graphene, diamonds, and fullerenes, with unique characteristics such as low dielectric constants, hydrocarbon nanomaterials have come to the forefront of negative electron affinity,largestericbulk,andelectron- material science. Numerous research works on their basic donating ability. They are widely used for advanced func- properties and potential applications have been carried out tional materials in nanocomposite science. Surface modifica- [1–4]. Diamondoids, which were first discovered and tion of diamondoids also produces functional derivatives that extracted from crude oil by Landa and Machacek in 1933 broaden its applications. This article provides a concise [5],arecage-shaped hydrocarbon molecules that resemble a review of the fundamentals of diamondoids, including diamond lattice structure [6]. These naturally abundant their origin and functionalization, electronic structure, hydrocarbon materials inherit some of the superior properties optical properties, and vibrational characteristics. The of diamonds, such as excellent thermal stability with a high recent advances of diamondoids and their derivatives in melting point, high hardness, and stiffness, as well as applications, such as nanocomposites and thin film coat- excellent chemical resistance. Unlike the detonation nano- ings, are presented. The fabrication of diamondoid-based diamond [7],theyhaveawell-defined molecular structure, nanostructured devices, including electron emitters, catalyst with high purity and homogeneity in size distribution [8].
    [Show full text]