Supramolecular synthons are the smallest structural units within which is encoded all the information inherent in the mutual recognition of. Supramolecular synthons in the gammahydroxybutenolides. A reranking of crystal structures was proposed by giving a preference to commonly occurring synthons in crystal structures of similar compounds 68. The functionalities on their framework drive the construction of the crystalline packing. A recurrent problem faced by the pharmaceutical industry when formulating drug products concerns poorly soluble drugs, which, despite having desirable pharmacological activity, present limited bioavailability. Pharmaceutical cocrystal formation represents a straightforward way to dramatically influence the solidstate properties of a drug substance, particularly its solubility and hence bioavailability. At the first level, only the hydrogenbonding capabilities of the amino and hydroxyl groups appear to be important. A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems. Desiraju described the significance of multipoint recognition supramolecular synthons. Download product flyer download highresolution cover. This book covers the hot topic of pharmaceutical salts and cocrystals focusing on the following essential aspects an overview of fundamental aspects on salts and cocrystals, racemic resolution via diastereomer separation, optimization of relevant physicochemical parameters and strengthening of intellectual property. Participants of the indofrench workshop on weak intermolecular interactions in february 2001.
Other readers will always be interested in your opinion of the books youve read. Bq part 1 book supramolecular chemistry has contents. Role of supramolecular synthons in the formation of the. Molecular recognition and selfassembly by nonamidic. Consistency and variability in these cocrystals containing positional isomers were found and analyzed. Lehn, together with pedersen and cram all three received the nobel prize in 1987, changed the paradigm of chemistry by stressing the importance of molecular recognition, which developed into the field he termed supramolecular chemistry. Hosseini strasbourg showed molecular networks assembled using programmed tectons and specific interaction patterns. Lehn cryptand synthesis an overview sciencedirect topics. This book covers the advances in the studies of hydrogenbondingdriven supramolecular systems made over the past decade. The supramolecular organization in the solid state of five novel gammahydroxybutenolides is described. Supramolecular chemistry embodies the creative power of chemistry. The synthon approach to csp mimics the molecular aggregation process, which is the assembling of molecules to a crystal via supramolecular synthondirected recognition. Supramolecular synthons and pattern recognition in adenine amides synthesis, structures and thermal properties ariel adamski faculty of chemistry, adam mickiewicz university, umultowska 89b, 61614 poznan, poland. Polynuclear aromatic hydrocarbons with curved surfaces.
Such patterns are termed supramolecular synthons and they depict the various ways in which complementary portions of molecules approach one another. Design of organic solids by edwin weber, 9783540646457, available at book depository with free delivery worldwide. Supramolecular recognition and energy frameworks in hostguest. The latter are prone to extensive cooperation and like a virtuoso play a symphony of life. While the extensive experimental and theoretical data available in the literature prove that hab and chb form twin supramolecular synthons in the solid, more experimental information has to become available before such a statement can be safely extended to interactions wherein elements of groups 14 and 15 are the electrophiles. Create an aipowered research feed to stay up to date with new papers like this posted to arxiv. The noncovalent bond is omnipresent in molecular systems at surfaces and the frontiers between materials in general. Crystal engineering and correspondence between molecular.
Glusker supramolecular synthons and pattern recognition a. Reviews supramolecular synthons in crystal engineeringa new organic synthesis gautam r. Supramolecular synthons and pattern recognition in adenine. Supramolecular synthons and pattern recognition in adenine amides synthesis, structures and thermal properties article in supramolecular chemistry 279. Desiraju, perspectives in supramolecular chemistry, wiley, chichester, 1996, vol. There are a vast number of hydrogenbonded synthons in crystal. A retrosynthetic dissection of a crystal structure into its constituent supramolecular synthons permits an identification of equivalent structures and, provided the levels of interaction insulation are high, crystal synthesis of these structures is possible.
A systematic structural study of halogen bonding versus. The structures, molecular recognition and selfassembly mechanism of supramolecular synthons in solution and in their corresponding cocrystals were verified by a combined experimental and theoretical calculation approach. Supramolecular synthons and pattern recognition hydrogenbonded ribbons, tapes and sheets as motifs for crystal engineering functional organic zeolite analogues crystalline polymorphism of organic compounds. The structure contained infinite 1d supramolecular chains held together by robust, primary oho chargeassisted hydrogen bonds, and the 2d sheet like pattern constructed via the expected carboxylpiperazine heterosynthon. Whether youve loved the book or not, if you give your honest and detailed thoughts then people will find new books that are right for them. Breaking motif 2 shown in the hydrogen bonding of 2 5 figure 3. In view of the patterns of supramolecular synthons in the cocrystal structures. Concepts, the supramolecular chemistry of lifenat, cation binding hosts, anion binding, ion pair receptors, molecular guests in solution, solid state inclusion compounds, crystal engineering. The prediction of the stability of hostguest complexes represents a great challenge to firstprinciples calculations due to an interplay of a wide variety of covalent and noncovalent interactions in these systems. Molecules free fulltext a supramolecular approach to. Carbohydratebased gelation gradually became a topic of interest with phenomenal research from yamasaki, hasoda, watanabe, shimizu 40,41, nolte, and most importantly, with the pioneering work of shinkai 43,44,45,46,47,48. Molecules free fulltext vibrational spectroscopy for. His specific supramolecular research foci are on macrocycles, cucurbiturils, fluorescent dye interactions, dispersion interactions, and waterbased assemblies. Crystal packing of 4 interrupting motif 2 8 figure 3.
Persistent nho interactions were found to play an important role in the formation of the final 3d arrays. Equivalence of molecular and supramolecular synthons. Current research in his group is focused on the study of halogen bonding synthons as well as crystal engineering of halogenbonded. The use of the supramolecular synthon concept facilitates such efforts and in this regard it may be mentioned that synthons combine topological characteristics with chemical information, thereby offering a simplification that is optimal to drawing such. The success of innovative drugs depends on an interdisciplinary and holistic approach to their design and development. Part of the topics in current chemistry book series topcurrchem, volume 198. Recognition of supramolecular synthons is based on the determination of specific intermolecular interactions like hydrogen or halogen bonds, stacking. The lively interest in organic solids stems from our increasing ability to manipulate and tune the properties of organic and organometallic materials e.
Indeed, it fashions entire new worlds that do not exist before they are shaped by the hand of the chemist, just as matter. An effective method for the synthesis of novel adenine amides was developed and successfully implemented, leading to. The chapters of this book provide an overview of supramolecular material assembly at various scales, including the formation of 2d polymers and molecular cages. Building upon desirajus concept of a supramolecular synthon, we. Cocrystallization is growing up as a possible approach to tackle this problem. Directional aspects of intermolecular interactions j. Thus, the design of effective ligands should be based on. The general principles of supramolecular chemistry sc were yet enunciated many years ago. An unprecedented ionic hydrogenbonded triplestranded helicate. In the last decades many efforts have been devoted to design supramolecular organocatalysts able to work in water as the reaction medium. Supramolecular synthons and pattern recognition springerlink.
In the simplest of cases benzoic, terephthalic, trimesic, and 1,3,5,7. General principles of supramolecular chemistry and molecular recognition. In this context, macrocyclic compounds played a role of primary importance thanks to their ease of synthesis and their molecular recognition. Each model tripeptide investigated has either a central pyridyl glycyl or a pyridyl alanyl residue between two terminally protected glycines. Paul a crystal of an organic compound is the ultimate supermolecule. Supramolecular synthons and pattern recognition in adenine amides. All tripeptides were coordinated to their complementary recognition unit, a. Studies that clearly address the balance between hbs and xbs are still quite unusual, but desiraju and coworkers examined supramolecular synthons created through anilinephenol interactions which included an analysis of the role played by secondary halogen bonds and. Supramolecular synthons in crystal engineeringa new. We use cookies to give you the best possible experience. Supramolecular synthons are the smallest structural units patterns, motifs. Considering the high level of our knowledge concerning covalent bond formation in the organic chemistry of molecules, our understanding of the principles involved in organic solid design is almost in its infancy. The study of anilinephenol recognition, in the context of crystal engineering and supramolecular synthons, has been an unusually complex exercise, considering the small size and relative simplicity of the nh 2 and oh functional groups.
The use of water as solvent provides promising benefits with respect to environmental impact. This article describes the synthesis and controlled assembly of four model biologicalhybrid scaffolds via coordination of a metal complex to four new tripeptides. The role of intermolecular interactions in solid and solution state selfassembly is discussed, as is the role of mechanochemistry on molecular and supramolecular architectures. Hydrogen bonded supramolecular structures zhanting li. The retrosynthesis of crystal structures in terms of robust supramolecular synthons recognition motifs and functionalised organic molecules building blocks has. Supramolecular structures by recognition and selfassembly of complementary partners.
Carbohydrate derived organogelators and the corresponding. The role of cocrystals in solidstate synthesis of imides. A detailed analysis of intermolecular interactions in crystals permits the definition of supramolecular synthons, structural units that more realistically display the recognition features between molecules. Therefore, the supramolecular synthon is a hbonding pattern composed of.
Iucr consistency and variability of cocrystals containing positional. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. Finally, the molecular recognition, selfassembly and evolution process of the. Contemporary approaches in material science and materials. Syntheses and analysis of supramolecular assemblies of 3,5dihydroxybenzoic acid and its bromo derivative with some ndonor compounds. The identification of synthons is then a key step in the design and analysis of crystal structures.
Hydrogenbonded ribbons, tapes and sheets as motifs for crystal engineering. For the last two decades gelators based on carbohydratederived low molecularweight compounds have gained the interest of several. Pdf supramolecular chemistry of modified amino acids and short. Desiraju hydrogenbonded ribbons, tapes and sheets as motifs for crystal engineering r. The journal of organic chemistry 2001, 66 14, 49304933. Pattern identification also leads to the possibility of comparison of crystal structures. Supramolecular synthons have been utilized for the controlled synthesis of onedimensional 1d, twodimensional 2d, and threedimensional 3d networks, many of which exhibit tailorable properties figure 16. By its very essence, by its ability to create and through the beauty of its objects, chemistry is an art as well as a science.
Full text of design of organic solids internet archive. Molecular recognition is therefore binding that serves a particular purpose. Comprehensive supramolecular chemistry ii sciencedirect. Cocrystals are crystalline materials comprising at least two components, solid at.
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