ISMSC 2007 - Università degli Studi di Pavia

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Complexity from Simple Parts via Subcomponent Self-Assembly Jonathan R. Nitschke * , Marie Hutin, David Schultz, Rupam Sarma and Victoria E. Campbell Organic Chemistry Department, University of Geneva, 30 quai Ernest-Ansermet, CH-1211 Genève 4 Highlights of some of our work in progress, as well as a few of the topics of the first four years of our research program, will be presented. 1 Starting with the use of the template effect to create stable structures linked together by both covalent (C=N) and coordinative (NM) bonds 2, 3 from mixtures of amines, aldehydes, and copper(I) ions, we have generated a variety of structures, including a tetrametallic grid held together by the hydrophobic effect, 4 helicates, 5, 6 macrocycles and catenates. 7 Four of these constructions are shown below. R N N Cu N N N N Cu N N N CuN N N R R N NCu N N R O O N N N Cu N N Cu N N N O O O O H N N H N N N Cu N N Cu N N N H N H N O O N N Cu N N N N Cu N N N N Cu N N The covalent imine (C=N) bonds that knit these structures together are thermodynamically stable, but capable of exchange with free amines. Differentials between the pKa’s of aliphatic and aromatic amines may be used as a driving force to effect selective imine exchange. As shown at right, protonated sulfanilic acid can displace the more basic aliphatic diamine a, which allows the deprotonated sulfanilate to incorporate itself in place of the diamine. If the pH of the reaction solution is raised, however, the reaction reverses: Deprotonated diamine a is 2 O 4 H 2N SO 3 - N N N Cu N N Cu N N N H3N NH3 a N N N Cu N N Cu N N N - O3S SO 3 - more nucleophilic than sulfanilate. Changes in pH may thus be used to switch between a closed macrocycle and open helicate. Current directions of our research program include the selection of specific structures from dynamic libraries, 3, 6, 8, 9 the preparation of conducting, metal-containing polymers, and the linking together of foldamers (in collaboration with Ivan Huc and Sijbren Otto) into assemblies having molecular weights and levels of structural definition comparable to those of proteins. 1. J.R. Nitschke Acc. Chem. Res. 2007, 40, 103 2. J.R. Nitschke Angew. Chem. Int. Ed. 2004, 43, 3073 3. D. Schultz, J.R. Nitschke Proc. Natl. Acad. Sci. U.S.A. 2005, 102, 11191 4. J.R. Nitschke, M. Hutin, G. Bernardinelli Angew. Chem. Int. Ed. 2004, 43, 6724 5. J.R. Nitschke, D. Schultz, G. Bernardinelli, D. Gérard J. Am. Chem. Soc. 2004, 126, 16538 6. M. Hutin, R. Franz, J.R. Nitschke Chem. Eur. J. 2006, 12, 4077 7. M. Hutin, C.A. Schalley, G. Bernardinelli, J.R. Nitschke Chem. Eur. J. 2006, 12, 4069 8. D. Schultz, J.R. Nitschke Angew. Chem. Int. Ed. 2006, 45, 2453 9. M. Hutin, G. Bernardenelli, J.R. Nitschke Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 17655 O H2N NH2 a O N Cu N I O O O O O H + 2 O + + O - O3S OH - IL 5 SO 3 - IL 6
Anion binding as a conformational and self-assembly trigger Jonathan W. Steed Chemistry Department, Durham University, Durham DH1 3LE, UK. Jon.steed@durham.ac.uk We have designed a number of anion-binding containers exhibiting dynamic conformational behaviour. These systems range from macrobicyclic cryptands (1) exhibiting conformational twisting to tripodal (2) and tetrapodal hosts (3) exhibiting significant flexibility of the pendant arms. The containers’ dynamic properties are modulated by anion binding. Anion binding may also be used to modulate self-assembly and hence rheological properties in supramolecular gel phase systems. This lecture explores the scope and uses of this kind of fundamental process in preparing new supramolecular sensors and materials. 1 2 3 HN N + N + NH N + HN R NH N + R O O N + O N + O O O HN NH O O R HN N + R IL 7 IL 8 Oligopyrrole-based chemosensors for potentially hazardous materials Jonathan L. Sessler † , Marcin Stpie † , Patricia Melfi † , Kent Nielsen †,‡ , Jan Jeppesen, ‡ Evgeny Katayev †,§ , Bertrand Donnio , Jackie Veauthier ° , and Andrew M. Shaw † Department of Chemistry & Biochemistry, The University of Texas at Austin, 1 University Station A5300, Austin, TX 78712-0165 USA ‡ Dept. of Physics and Chemistry, University of Southern Denmark, Campusvej 55, DK-5230, Odense M, Denmark § Institute for Organoelement Chemistry, Russian Academy of Sciences, Vavilova st. 28, Moscow, 119991, Russia Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 (CNRS-Université Louis Pasteur), 23 rue du Loess BP 43, 67034 Strasbourg Cedex 2, France ° C-IIAC (Inorganic, Isotope, & Actinide Chemistry), Los Alamos National Laboratory, MS J514, Los Alamos, NM 87545, USA EvanesCo Ltd, 4 &5 Forde Court, Forde Road, Newton Abbot, TQ12 4AD, United Kingdom The design and synthesis of novel receptors with the ability to recognize selectively and signal selected analytes through easy-to-visualize changes in color constitutes a critical goal in macrocyclic and supramolecular chemistry. We have approached this broad objective via the construction of both cyclic and acyclic pyrrole-based receptors that are able to interact with cationic, anionic, and neutral substrates through various combinations of metal coordination, hydrogen bonding, electrostatic, and donor-acceptor interactions. In this presentation the focus will be on systems, such as those shown in Figure 1, that allow for the specific colorimetric detection of potentially hazardous analytes, including such canonical risks as high-valent radioactive actinide cations, the pertechnetate anion, and electron deficient nitroarene explosives. Several lead references are given below. The work in the presenter’s laboratory was supported by the National Institutes of Health, the National Science Foundation, and the U.S. Department of Energy. NH NH HN N H N N isoamethyrin Ph Ph O N N O H H NH HN N NH HN BP-DPM R N NH HN NH HN NH N HN R R R R R R R R R R R R R R R cyclo[8]pyrrole Figure 1: Novel receptors and sensors relevant to this presentation. N S S Me Me Me Me N S H S S NH HN S H S S N Me Me Me Me S S [1] Nielsen, K. A.; Cho, W.-S.; Jeppesen, J. O.; Lynch, V. M.; Becher, J.; Sessler, J. L. J. Am. Chem.Soc. 2004, 126, 16296-16297. [2] Sessler, J. L.; Katayev, E. A.; Pantos, G. D.; Reshetova, M. D.; Khrustalev, V. N.; Lynch, V. M.; Ustynyuk, Y. A. Angew. Chem. Int. Ed. 2005, 44, 7386-7390. [3] Stpie, M.; Donnio, B.; Sessler, J. L. Angew. Chem. Int. Ed. 2007, 46, 1431–1435. [4] Sessler, J. L.; Melfi, P. J.; Seidel, D.; Gorden, A. V.; Ford, D. K.; Palmer, P. D.; Tait, C. D. Tetrahedron, 2004, 60, 11089-11097. PrS PrS S S PrS SPr S PrS S S S SPr TTF calix[4]pyrrole SPr SPr
Page 1 and 2: nd International Symposium on Macro
Page 3 and 4: Eric Anslyn University of Texas at
Page 5 and 6: 1 Map of Salice Terme 7 5 6 3 9 2 8
Page 7 and 8: Symposium Program All sessions will
Page 9 and 10: 11:40 - 12:00 Oral Presentation: V.
Page 11 and 12: PSA 22 Anion Receptors Based On The
Page 13 and 14: PSA 72 Molecular Tectonics: STM Stu
Page 15 and 16: PSB 11 Dual binding properties of p
Page 17 and 18: PSB 57 Removal Of Heavy Metal Ions
Page 19 and 20: 40 years of polyazamacrocycles. A p
Page 21 and 22: PL 5 Anion-Templated Assembly of In
Page 23 and 24: Exercising Demons: Synthetic Molecu
Page 25: Synthetic Strategies and Structural
Page 29 and 30: Supramolecular control of a metal c
Page 31 and 32: OP 3 Control of molecular architect
Page 33 and 34: Catalyst discovery using dynamic co
Page 35 and 36: Cucurbit[n]uril Molecular Container
Page 37 and 38: OP 15 From non-mesomorphic nature t
Page 39 and 40: OP 19 Pyrrolic Tripodal Receptors f
Page 41 and 42: PSA 1 Efficient synthesis of pseudo
Page 43 and 44: Tetra-Cationic phthalocyanines Yasi
Page 45 and 46: PSA 9 Cell penetrating borosilica n
Page 47 and 48: PSA 13 Halide anion interactions wi
Page 49 and 50: Sensing with cavitands: Moving from
Page 51 and 52: Lead(II) complexation by calix[4]-h
Page 53 and 54: Functional [2×2] Grids Xiao-Yu Cao
Page 55 and 56: Neutral supramolecular systems inco
Page 57 and 58: PSA 33 Ratiometric Ion Sensors by R
Page 59 and 60: A photocontrollable receptor for Cu
Page 61 and 62: New emitters for mass spectrometric
Page 63 and 64: PSA 45 A fast-moving electrochemica
Page 65 and 66: Macrocyclic Porphyrin-Bidentate Che
Page 67 and 68: PSA 53 Electronic spectroscopy of e
Page 69 and 70: PSA 57 Self-assembly of calixarene/
Page 71 and 72: PSA 61 Piperazine Containing Polyam
Page 73 and 74: PSA 65 Synthesis of Self-Assembly S
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Supra-Biomolecular Tandem Assays -
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PSA 77 Synthesis and molecular reco
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PSA 81 Reaction of phthalic aldehyd
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Binding of perrhenate and pertechne
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PSA 89 Supramolecular assemblies of
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Polytopic Ligands for the Recovery
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PSB 1 Rosette Nanotubes as Scaffold
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PSB 5 Towards the development of ne
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PSB 9 A Quantitative [2]Rotaxane Sy
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Metal Complexes of the Polyether Io
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PSB 17 Metal controlled anion inter
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Crown Ether-tert-Ammonium Salt Comp
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PSB 25 A Minimalist Design for Self
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PSB 29 Control of Translation of th
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PSB 33 Multinuclear NMR, ESI MS and
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PSB 37 New Anthracene-based cycloph
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PSB 41 1,3,5-Tris(2-aminophenyl)ben
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Simple Isophthalamide Derivatives A
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PSB 49 On Sokolov’s approach to a
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PSB 53 New chromogenic sensors usin
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PSB 57 Removal of heavy metal ions
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PSB 61 Molecular Recognition of Ele
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PSB 65 Switching of Self to non-Sel
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Investigation of -cyclodextrin bind
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Novel ditopic probes for different
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PSB 77 Synthesis, supramolecular ar
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PSB 81 Tripodal polyamines as anion
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PSB 85 Templated Synthesis of Large
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PSB 89 Direct C-C coupling of 1,2,4
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PSB 93 The study of cytotoxicity ef
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PSB 97 Development of innovative so
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Campbell B. PSA 39 Campbell F. PSB
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Jensen L.G. PSA 82 Jeppesen J.O. IL
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Peters A.J. PSB 39 Peters A.J. PSB
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Sponsors of ISMSC 2007 The contribu
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