CHMY 562.01: Organic Structure and Mechanism
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Part III Project 2016/17 Professor Chris Hunter Physical Organic
Department of Chemistry: Part III Project 2016/17 Professor Chris Hunter Physical Organic Chemistry or Synthetic Supramolecular Chemistry EMAIL [email protected] Group web site http://www-hunter.ch.cam.ac.uk/ Contact details: I will be available to discuss projects on Monday 15th May (please email to make an appointment) The success of synthetic chemistry in the last century was built on the development of a set of design rules that allowed the quantitative prediction of reactivity and conformation based simply on chemical structure. The goal of our research is to establish a comparable set of rules that can be used for the design of non-covalent systems with equal reliability. Research projects are available in different areas and can be tailored to involve combinations of different techniques: organic synthesis; coordination chemistry; structural and thermodynamic characterisation of intermolecular complexes using NMR spectroscopy, mass spectrometry, X-ray crystallography; high-throughput physical organic chemistry; molecular design and molecular modelling. Physical Organic Chemistry: Quantitative Non-Covalent Chemistry Synthetic supramolecular systems are ideally suited for the systematic study and quantitative determination of the thermodynamic properties of non-covalent interactions. We are developing new experimental methods for quantifying the relative contributions of different factors that influence the behaviour of complex systems. By characterising the relationship between chemical structure and thermodynamic properties, we aim to develop rules of thumb (and software) for predicting the properties of molecular systems based on a quantitative fundamental understanding of non-covalent interactions. This project will involve some synthetic chemistry, but the focus will be on quantitative physical measurements using a variety of spectroscopic techniques and instrumentation as well as mathematical model building. -
Supramolecular Catalysts Green Chemistry
139 7 Supramolecular Catalysis as a Tool for Green Chemistry Courtney J. Hastings 7.1 Introduction Catalysis is central to advancing green chemistry in the area of synthetic chemis- try [1,2]. Beyond replacing stoichiometric reagents, catalysts have the potential to streamline multistep synthesis by enabling new bond-forming processes to shorten synthetic sequences and achieve better step economy [3,4]. Supra- molecular catalysis and the application of supramolecular concepts to catalytic reactions is emerging as a valuable tool for improving catalytic reactions for syn- thetic chemistry. Supramolecular catalysis can enable aqueous reaction condi- tions, improve reactions selectivity, improve catalyst lifetime, and enable tandem reactions, all of which can have positive impacts on the cost, waste, and energy associated with a reaction. The field of supramolecular chemistry concerns the design of molecular enti- ties that are defined by reversible, noncovalent interactions. While each supra- molecular interaction is quite weak individually, the effect of many such interactions working in concert can produce strongly associated and structurally well-defined molecular species [5–7]. Such additive effects are responsible for the spectacular structural complexity found in biomacromolecules such as pro- teins. Efforts to characterize these interactions have provided chemists with a “toolbox” of reliable methods to program the association between two or more molecules to form a single complexed species. Thus, supramolecular chemistry represents a complementary approach toward molecular construction, and one that offers certain advantages over covalent chemistry [5–8]. Like supramolecular interactions, host–guest binding relies on manifold non- covalent interactions, with the added requirement that the host possess an inte- rior cavity that is complementary in size and shape to the guest molecule [9–11]. -
Professor of Chemistry
Bruce C. Gibb FRSC Professor of Chemistry Department of Chemistry Tulane University New Orleans, LA 70118, USA Tel: (504) 862 8136 E-mail: [email protected] Website: http://www.gibbgroup.org Twitter: @brucecgibb Research Interests: Aqueous supramolecular chemistry: understanding how molecules interact in water: from specific ion- pairing and the hydrophobic effect, to protein aggregation pertinent to neurodegenerative disorders. Our research has primarily focused on: 1) novel hosts designed to probe the hydrophobic, Hofmeister, and Reverse Hofmeister effects, and; 2) designing supramolecular capsules as yocto-liter reaction vessels and separators. Current efforts to probe the hydrophobic and Hofmeister effects include studies of the supramolecular properties of proteins. Professional Positions: Visiting Professor, Wuhan University of Science and Technology as a Chair Professor of Chutian Scholars Program (2015-2018) Professor of Chemistry, Tulane University, New Orleans, USA (2012-present). University Research Professor, University of New Orleans, USA (2007-2011). Professor of Chemistry, University of New Orleans, USA (2005-2007). Associate Professor of Chemistry, University of New Orleans, USA (2002-2005). Assistant Professor of Chemistry, University of New Orleans, USA, (1996-2002). Education: Postdoctoral Work Department of Chemistry, New York University. Synthesis of Carbonic Anhydrase (CA) mimics with Advisor: Prof. J. W. Canary, (1994-1996). Department of Chemistry, University of British Columbia, Canada De Novo Protein development. Advisor: Prof. J. C. Sherman (1993-1994). Ph.D. Robert Gordon’s University, Aberdeen, UK. Synthesis and Structural Examination of 3a,5-cyclo-5a- Androstane Steroids. Advisors: Dr. Philip J. Cox and Dr. Steven MacManus (1987-92) . B.Sc. with Honors in Physical Sciences Robert Gordon’s University, Aberdeen, UK. -
Supramolecular Chemistry: Functional Structures on the Mesoscale
From the Academy Supramolecular chemistry: Functional structures on the mesoscale SonBinh T. Nguyen*, Douglas L. Gin†, Joseph T. Hupp*, and Xi Zhang‡ *Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113; †Departments of Chemical Engineering, Chemistry, and Biochemistry, University of Colorado, Boulder CO 80309; and ‡Department of Chemistry, Jilin University, Changchun 1300023, People’s Republic of China Supramolecular chemistry deals with the chemistry and collective behavior of organized ensembles of molecules. In this so-called mesoscale regime, molecular building blocks are organized into longer-range order and higher-order functional structures via comparatively weak forces. As one of the modern frontiers in chemistry, supramolecular chemistry heralds many promises that range from biocompatible materials and biomimetic catalysts to sensors and nanoscale fabrication of electronic devices. or over 100 years, chemistry has focused primarily on un- nanoscale and microscale ordering. During the last decade, this idea Fderstanding the behavior of molecules and their construction has been successfully demonstrated by a number of researchers. from constituent atoms. Our current level of understanding of Lastly, the need for improved miniaturization and device molecules and chemical construction techniques has given us the performance in the microelectronics industry has inspired many confidence to tackle the construction of virtually any molecule, investigations into supramolecular chemistry. It is conceivable be it biological or designed, organic or inorganic, monomeric or that ‘‘bottom up’’ materials fabrication approaches based on macromolecular in origin. During the last few decades, chemists supramolecular chemistry will provide a solution to the antici- have extended their investigations beyond atomic and molecular pated size limitations of ‘‘top down’’ approaches, such as pho- chemistry into the realm of supramolecular chemistry. -
Supramolecular Studies on the Behaviour of Different Chiral
ADVERTIMENT. Lʼaccés als continguts dʼaquesta tesi queda condicionat a lʼacceptació de les condicions dʼús establertes per la següent llicència Creative Commons: http://cat.creativecommons.org/?page_id=184 ADVERTENCIA. El acceso a los contenidos de esta tesis queda condicionado a la aceptación de las condiciones de uso establecidas por la siguiente licencia Creative Commons: http://es.creativecommons.org/blog/licencias/ WARNING. The access to the contents of this doctoral thesis it is limited to the acceptance of the use conditions set by the following Creative Commons license: https://creativecommons.org/licenses/?lang=en ,IDF5AC@97I@5FGHI8=9G CBH<9 69<5J=CIF C:8=::9F9BH7<=F5@ 7M7@C5@?5B9 65G987CADCIB8G5G F979DHCFG ;9@5HCFG5B8GIF:57H5BHG 9FB5H)= =C@985 -9G=C7HCF5@ GHI8= 89C7HCF5H9B*IVA=75 ,ID9FJ=G986M )FC: /=79BSF5B7<589@@ 5@@C )FC: +CG5&ª (FHIYC&=B;5FFC 9D5FH5A9BH89*IVA=75 57I@H5H89=TB7=9G -BJzOF>MOBPBKQ>A> MBO>PMFO>O>IDO>RAB$L@QLOMBO 9FB5H)= = C@985 4EFPQEBPFPFPMOBPBKQBACLODO>AR>QFLK>P$L@QLO?V 9FB5H)= = C@985 6FPQFMI>R 2B>A>KA>MMOLSBA 0OLC 6F@BKq"O>K@E>ABII'>IIL 0OLC 2LP>-X/OQRxL-FKD>OOL "BII>QBOO> ABPBQBJ?OBAB "BII>QBOO> QE LC 3BMQBJ?BO 6GHF57H )K QEFP QEBPFP CLRO AFCCBOBKQ PRMO>JLIB@RI>O PVPQBJP TBOB PQRAFBA >P OB@BMQLOP DBI>QLOP LO PROC>@Q>KQP 4EB FKCIRBK@B LC AFCCBOBKQ PQOR@QRO>I C>@QLOP LC QEB PFKDIB JLIB@RIB LK QEB CFK>I PRMO>JLIB@RI>O MOLMBOQFBP T>P >K>IVPBA $FCCBOBKQ PQO>QBDFBP TBOB RPBA QL MOBM>OB QEB PQRAFBA @LJMLRKAP 4EB @LJ?FK>QFLK LC AFCCBOBKQ QB@EKFNRBP IB>AP RP QL?BQQBO RKABOPQ>KA QEBPB PVPQBJP L?Q>FKFKD PVKBODFPQF@ -
Supramolecular Recognition: on the Kinetic Lability of Thermodynamically Stable Host–Guest Association Complexes
Supramolecular recognition: On the kinetic lability of thermodynamically stable host–guest association complexes Andrew J. Goshe*, Ian M. Steele*, Christopher Ceccarelli†, Arnold L. Rheingold†, and B. Bosnich*§ *Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637; and †Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 Edited by Jack Halpern, University of Chicago, Chicago, IL, and approved January 16, 2002 (received for review November 2, 2001) A molecular receptor consisting of a spacer bearing two cofacially Table 1. Supramolecular assembly bonds disposed terpyridyl–palladium–ligand (terpy-Pd-L) units rigidly sepa- rated by about 7 Å has been investigated for molecular recognition of planar aromatic molecules. It is found that although the receptor forms stable 1:2 host–guest association complexes with 9-methylan- thracene (9-MA), the guest undergoes very rapid site exchange within the receptor and with external free 9-MA. A crystal structure of the 2:1 adduct shows one 9-MA in the molecular cleft defined by the two terpy-Pd-L units and the other resides on an outside face of one terpy-Pd-L unit. To establish the site residency time of the guests, a number of tethered molecules were prepared. These involve an anthracene molecule tethered to a pyridine ligand bound to the palladium atoms to form intramolecular host–guest adducts. Rotating-frame Overhauser effects were used to infer the site resi- many third row transition metal bonds are stable and nonlabile, dency of the anthracene guests in the receptor. Variable-temperature and such bonds are used as the permanent components of 1H NMR spectroscopy of the intramolecular host–guest complexes supramolecular structures. -
Supramolecular Chemistry of Nanomaterials
Supramolecular Chemistry of Nanomaterials Joachim Steinke Ramon Vilar Department of Chemistry Imperial College of Science, Technology and Medicine [email protected] [email protected] Topics to be covered in the course: 1 - Introduction (definition of terms, etc.) 2 – Self-assembly 3 – Nano-capsules for delivery and reactions 4 – Supramolecular Switches 5 – Molecular Machines 6 – Self assembly in surfaces 7 – Supramolecular chemistry of polymeric materials General references on Supramolecular Chemistry • J.L. Atwood, J.E.D. Davies, D.D. MacNicol, F. Vogtle (editors), Comprehensive Supramolecular Chemistry, Elsevier, Oxford 1996 • J.W. Steed, J.L. Atwood, Supramolecular Chemistry, Wiley, 2000 • P.D. Beer, P.A. Gale, D.K. Smith, Supramolecular Chemistry, OCP, 1999 • A. Bianchi, K. Bowman-James, E. Garcia-España (editors), Supramolecular Chemistry of Anions, Wiley-VCH, New York 1997 • J.F. Stoddart (editor), Monographs in Supramolecular Chemistry, RSC • J.M. Jehn, Supramolecular Chemistry, VCH, Weinheim 1995 • J.P. Behr (editor), The lock and key principle, Wiley, Guilford 1994 Nanomaterials Nanoscale materials; materials with structural features (particle size or grain size, for example) of at least one dimension in the range 1-100 nm. What makes these nanomaterials so different and so intriguing? Their extremely small feature size is of the same scale as the critical size for several physical phenomena. http://www.csa.com/hottopics/nano/overview.html Scientists want to know how simple atoms and molecules come together and arrange themselves to form complex systems, such as living cells that make life possible on earth. This "bottom-up" science, which deals with how complex systems are built from simple atomic-level constituents, spawned nanoscience. -
Advances in Molecular and Supramolecular Fullerene Chemistry
thermal treatment of 1,6-fullerenynes (1) affords cyclobutene adducts (3) without the presence of a catalyst; in a reaction this is the first example of a thermal [2+2] cyclization involving a fullerene double bond as the alkene moiety of the reactive 1,6-enyne7 (Fig. 1). A recent example of an unknown chemical reactivity has been found in fulleropyrrolidines, which are among the most studied fullerene derivatives used for many applications in materials science as well as in the search for biological properties.8 In contrast to Advances in Molecular other labile fullerene cycloadducts such as those prepared from Diels-Alder or Bingel reactions,1 fulleropyrrolidines and Supramolecular have been considered to be stable fullerene derivatives. However, the Fullerene Chemistry thermal quantitative retro-cycloaddition of fulleropyrrolidines to obtain the by Nazario Martín, Nathalie Solladié, and Jean-François Nierengarten pristine fullerene together with its typical magenta color in solution (Fig. 2) n 1996 Sir Harold W. Kroto, Robert discipline, a wide variety of important has been reported only recently.9 This F. Curl, and the late Richard E. reactions involving alkenes and alkynes reaction reveals that the understanding I Smalley received the Nobel Prize for have not been studied previously on of the reactivity of fullerene derivatives the discovery of the fullerenes. After the fullerene surface. One example is still far from the level where it is a decade, these round-shaped carbon of the most successful reactions in possible to predict -
When Molecular Magnetism Meets Supramolecular Chemistry: Multifunctional and Multiresponsive Dicopper(II) Metallacyclophanes As
magnetochemistry Review When Molecular Magnetism Meets Supramolecular Chemistry: Multifunctional and Multiresponsive Dicopper(II) Metallacyclophanes as Proof-of-Concept for Single-Molecule Spintronics and Quantum Computing Technologies? Renato Rabelo 1, Salah-Eddine Stiriba 1 , Danielle Cangussu 2 , Cynthia L. M. Pereira 3 , Nicolás Moliner 1, Rafael Ruiz-García 1,*, Joan Cano 1,*, Juan Faus 1, Yves Journaux 4 and Miguel Julve 1,* 1 Instituto de Ciencia Molecular (ICMol), Universitat de València, Paterna, 46980 València, Spain; [email protected] (R.R.); [email protected] (S.-E.S.); [email protected] (N.M.); [email protected] (J.F.) 2 Instituto de Química, Universidade Federal de Goiás, Goiânia-GO 74001-970, Brazil; [email protected] 3 Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, Pampulha, Belo Horizonte, Minas Gerais 31270-901, Brazil; [email protected] 4 Institut Parisien de Chimie Moléculaire, Sorbonne Universités UPMC Univ Paris 06, 75005 Paris, France; [email protected] * Correspondence: [email protected] (R.R.-G.); [email protected] (J.C.); [email protected] (M.J.) Received: 10 November 2020; Accepted: 2 December 2020; Published: 4 December 2020 Abstract: Molecular magnetism has made a long journey, from the fundamental studies on through-ligand electron exchange magnetic interactions in dinuclear metal complexes with extended organic bridges to the more recent exploration of their electron spin transport and quantum coherence properties. Such a field has witnessed a renaissance of dinuclear metallacyclic systems as new experimental and theoretical models for single-molecule spintronics and quantum computing, due to the intercrossing between molecular magnetism and metallosupramolecular chemistry. -
COPYRIGHTED MATERIAL 2 Concepts
Concepts 1 ‘Mankind is divisible into two great classes: hosts and guests.’ Max Beerbohm (b. 1872), Hosts and Guests COPYRIGHTED MATERIAL 2 Concepts 1.1 Defi nition and Development of Supramolecular Chemistry Lehn, J.-M., ‘Supramolecular chemistry and self-assembly special feature: Toward complex matter: Supramolecular chemistry and self-organization’, Proc. Nat. Acad. Sci. USA, 2002, 99, 4763–4768. 1.1.1 What is Supramolecular Chemistry? Supramolecular chemistry has been defi ned by one of its leading proponents, Jean-Marie Lehn, who won the Nobel Prize for his work in the area in 1987, as the ‘chemistry of molecular assemblies and of the intermolecular bond’. More colloquially this may be expressed as ‘chemistry beyond the molecule’. Other defi nitions include phrases such as ‘the chemistry of the non-covalent bond’ and ‘non-molecular chemistry’. Originally supramolecular chemistry was defi ned in terms of the non-covalent interaction between a ‘host’ and a ‘guest’ molecule as highlighted in Figure 1.1, which illustrates the relationship between molecular and supramolecular chemistry in terms of both structures and function. These descriptions, while helpful, are by their nature noncomprehensive and there are many exceptions if such defi nitions are taken too literally. The problem may be linked to the defi nition of organometallic chemistry as ‘the chemistry of compounds with metal-to-carbon bonds’. This immediately rules out Wilkinson’s compound, RhCl(PPh3)3, for example, which is one of the most important industrial catalysts for organometallic transformations known in the fi eld. Indeed, it is often the objectives and thought processes of the chemist undertaking the work, as much as the work itself, which determine its fi eld. -
The Rise of Supramolecular Chemistry in Industry
EDITORIAL RINUS BROXTERMAN Member of Chimica Oggi/Chemistry Today Scientific Advisory Board DSM Chemical Technology R&D B.V., Urmonderbaan 22, 6167 RD Geleen, Netherlands Rinus Broxterman The rise of supramolecular chemistry in industry The relevance of non-covalent molecular interactions is apparent in our daily life: they play crucial roles in natural occurring systems such as in photosynthesis, protein folding, and indeed the action of a cell as a whole. Furthermore, these interactions have also proven their potential in industrial applications as they have played – and are still playing – an important role in ascertaining the desired properties of the functional assemblies/products created. En route to realizing its full potential it is not surprising that in the last two decades a tremendous boost in academic contributions has been observed, resulting in a status of supramolecular chemistry leaving its embryonic development phase. A major reason for this development is that the underlying scientifi c themes and challenges are being unravelled and mastered. Most importantly, the fi eld is unfolding its true strength in the ability to upfront design non-covalent interactions in the molecular structure to steer the assembly of molecules towards a morphology (mesoscopic structure) that – in its turn – is required to deliver the desired macroscopic properties. As a result of this ability, supramolecular chemistry has the potential to act across the design chain of many different types of products, linking the fundamentals of molecular chemistry to product development (and the value chain from small molecule building blocks to full macroscopic products). The consequence of linking the molecular scale to the macroscopic scale is that knowledge from both ends of the spectrum are necessary to be successful. -
The Supramolecular Chemistry of Cucurbituril Molecules
THE SUPRAMOLECULAR CHEMISTRY OF CUCURBITURIL MOLECULES SUSANA LORENZO A thesis submitted in fulfilment Of the requirements for the degree of Doctor of Philosophy School of Chemistry University of New South Wales March, 2006 Page i ABSTRACT The set of molecules cucurbit[n]uril (Qn) are macrocycles composed of n glycoluril monomers linked by methylene groups. These molecules have two oxygen-ringed portals of a diameter slightly smaller than their internal cavity diameter. This thesis describes syntheses, crystallisations, crystal structure determinations, crystal packing analyses and force field calculations exploring the supramolecular chemistry of Qn molecules and their derivatives. Qn acts as a host for guest molecules and at the outset of this project no metal containing molecule had been encapsulated in a Qn molecule. One aim of this project was to prepare such complexes. This was achieved with the synthesis and characterisation of crystalline {[cis-SnCl4(H2O)2]@Q7}2(SnCl6)3(H3O)6(H2O)23. Other compounds prepared and characterised crystallographically in the course of this project are: [(Q6)(Na3(H2O)8)]2[CoCl4]4[Co(H2O)6]2[CoCl(H2O)5]2(Cl)4, (Q5@Q10)(CH3COOH)(Cl)2(H3O)2(H2O)26, (Cl@Q5)4Q6(SnCl6)8(H3O)20(H2O)24, (Q8)3(PtCl6)4(H3O)8(H2O)x, (Q8)2(PtCl6)3(H3O)6(H2O)18, (Q7)(Cr3O10)(H3O)2(H2O)x and (Q6)(SnCl6)(H3O)2(H2O)x. While the smaller Qn (n = 5–8) retain their circular forms, the larger Qn (n > 8) are less rigid and distort to accommodate larger guests. After analysis of the crystal structures of these Qn compounds and those listed in the Cambridge Structural Database, the principal packing motifs of the Qn molecules were elucidated.