The halogen bond in the design of functional supramolecular materials. Halogen bonding as a new driving force for layerbylayer. Halogen bonding xb has been recently exploited as a significant tool for engineering crystals involving coordination and organometallic compounds as tectons. In the same line, we have demonstrated recently that both e4,4di. Request pdf halogen bonding in supramolecular chemistry halogen bonding is the noncovalent interaction where halogen atoms function as electrophilic species. Recently, halogen bonding has been introduced in the field of supramolecular rotators, in configurations such as the molecular rotor on axle 35,36 and a molecular top 37. The energetic and geometrical features of the interaction are described along with the atomic characteristics that confer molecules with the specific ability to interact through this interaction. Synergistic effects of hydrogen and halogen bonding in cocrystals of dipyridylureas and diiodotetrafluorobenzenes. Pdf halogen bonding xb, as a directional interaction between covalently bound halogen atoms xb donor. The halogen bond is well known for its ability to assemble supramolecules. The use of halogen bonding as a tool to construct a catalyst backbone is reported. To identify the effects of halogen bonding in the architecture of schiff base complex supramolecular networks, we introduced halogenated schiffbase 3br5clsalen as ligand and isolated a new salentype manganeseiii complex mn iii clh 2 o3br5clsalen 1 where 3br5clsalen n,nbis3bromo5chlorosalicylidene1,2diamine.
Supramolecular chemistry is an uptodate, integrated textbook that tells the. Abstract the term halogen bonding describes the tendency of halogen atoms to interact with lone. Halogen bonding in supramolecular and solid state chemistry faraday discussion. The subtle balance of weak supramolecular interactions. A new approach for fabricating a layerbylayer polymer film was explored, which was based on the halogen bonding between poly44iodo2,3,5,6tetrafluorophenoxybutyl acrylate and poly4vinylpyridine. Iucr a systematic structural study of halogen bonding. Nov, 2018 halogen bonding directed supramolecular quadruple and double helices from hydrogen. Bonding interactions directed 2d crystalline supramolecular j. A powerful tool in intermolecular halogen bonding in solution chemistryopen 2020, doi. Sep 01, 2015 this attention to halogen bonding is fully justified given its importance in supramolecular synthesis, materials chemistry, biological systems and drug design bauza et al.
Halogen bonding is the noncovalent interaction where halogen atoms function as electrophilic species. Thus, halogen bonding may play a role in both assembly and promoting dynamical processes. In recent years, halogen bonding has grown from a scientific curiosity to one of the most interesting noncovalent interactions for constructing supramolecular assemblies. Specifically, pyridyl and iodotetrafluoroarylsubstituted phosphines were assembled in the presence of a rhodiumi precursor to form the corresponding halogen bonded complex xbphosrh. Supramolecular arrangements in organotellurium compounds te. Foster, katharina fucke, pierangelo metrangolo, giuseppe resnati and jonathan w. The binding features and structural properties of halogen bonding are discussed and applied to drive the intermolecular self. Halogen bonding directed supramolecular quadruple and.
A study is conducted to investigate halogen bonding in supramolecular chemistry. Supramolecular synthesis is typically limited to onepot reactions because of the reversibility of noncovalent bonds, and to overcome this restriction we need to be able to rank the relative structural importance of such interactions and build synthetic methods to utilize synthons which can operate sidebyside without interference. Legon halogen bonding in solution, mate erdelyi unconventional motifs for halogen bonding, by kari rissanen halogen bonding in supramolecular synthesis, christer aakeroy halogen bond in synthetic organic chemistry, stefan m. The presence of fluorine substituents a most popular 20182019 supramolecular chemistry articles. Halogen bonding has emerged as a promising tool in the toolbox of supramolecular chemists and crystal engineers. Towards engineering of solidstate supramolecular rotors. Halogen bonding in the molecular recognition of thyroid. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a twocomponent gel cogel is essentially unexplored, and forms the basis for this study. Specifically, pyridyl and iodotetrafluoroarylsubstituted phosphines were assembled in the presence of a rhodiumi precursor to form the corresponding halogenbonded complex xbphosrh. The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts kari raatikainen, massimo cametti and kari rissanen full research paper open access address. Supramolecular chemistry is chemistry beyond the molecule the chemistry of molecular assemblies and intermolecular bonds.
Jul 29, 2008 halogen bonding is the noncovalent interaction where halogen atoms function as electrophilic species. Jingxiang lin, yu chen, dan zhao, xiuqiang lu, yuanzhi lin. Layerbylayer assembly of two polymers was confirmed by uv. Halogen bonding has an impact on all research fields where the control of intermolecular recognition and selfassembly processes plays a key role. Halogenbonded, eightfold ptstype interpenetrated supramolecular network. Halogen bonding as a supramolecular dynamics catalyst. Halogen bonding directed supramolecular quadruple and double. Supramolecular arrangements in organotellurium compounds via te halogen contacts 117 structures containing tellurium atoms with only three halogen atoms bonded to it, i. In halogen bonding, a halogen atom acts as an electrophile, or electronseeking species, and forms a weak electrostatic interaction with a nucleophile, or electronrich species. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. Supramolecular chemistry is an uptodate, integrated textbook that tells the newcomer to the field everything. Zhi liu department of chemistry, shanghai key laboratory, of molecular catalysis and innovative materials, and, collaborative innovation centre of chemistry, for energy materials ichem fudan university, 2205 songhu road.
Halogenbondingtriggered supramolecular gel formation. Halogen bonding as a supramolecular dynamics catalyst nature. Frontiers covalent and noncovalent noble gas bonding. Halogen bonding in supramolecular synthesis springerlink. We have reported conducting nanowire and its sheath, both integrated in a crystal structure as shown in figure 1 ref. The halogen bond in the design of functional supramolecular. A systematic structural study of halogen bonding versus. Xy interaction wherein x is an electrophilic halogen atom lewis acid, halogen bonding donor, d is an electron density donor lewis base, halogen bonding acceptor and y is c, n, halogen, etc. Now, halogen bonding the attractive interaction between an electrondeficient. Dec 23, 2019 halogen bonding xb is an attractive interaction between a halogen atom and an electron donor. Fluorinated azobenzenes as supramolecular halogenbonding. Though similar to the more familiar hydrogen bonding, four primary differences between these two interactions make halogen bonding a unique tool for.
Supramolecular chemistry is an uptodate, integrated textbook that tells the newcomer to the field everything they need to know to get started. Halogen bonding in metalorganicsupramolecular networks. Halogen bonding in supramolecular chemistry halogen bonding in supramolecular chemistry metrangolo, pierangelo. The ability to achieve strong molecular recognition in water is a key challenge for supramolecular chemistry. Halogen atoms are typically located at the periphery of organic molecules and. Special issue halogen bonding in supramolecular self. Her research interests are in the area of supramolecular chemistry and include exploiting halogen bonding for molecular recognition and anion templation. Halogen bonding in supramolecular chemistry wiley online library.
The energetic and geometrical features of the interaction are described along with the. The study gives an overview of how computational methods have been applied to understand the nature of halogen. In both cases, a the hydrogenhalogen bond acceptor is the atom, group, or molecule that donates electrons to the electron poor species hd or xd the hydrogen or halogen bond donors respectively. Huber anion recognition in solution via halogen bonding, mark s. The study gives an overview of how computational methods have been applied to understand the nature of. Halogen bonding in supramolecular and solid state chemistry home. Aug 04, 2008 halogen bonding in supramolecular chemistry metrangolo, pierangelo. Request pdf halogen bonding in supramolecular chemistry halogen bonding is the noncovalent interaction where halogen atoms function. The nucleophilic agent in these interactions tends to be highly electronegative such as oxygen, nitrogen, or sulfur, or may be anionic, bearing a negative formal.
Halogen bonding provides heterooctameric supramolecular. Halogen bonding in supramolecular chemistry request pdf. Halogen bonding xb is an attractive interaction between a halogen atom and an electron donor. The crystal structure of the newly synthesized 4methoxyphenylphenyliodonium thiocyanate, phi4c6h4omescn, represents the first example of 16membered cyclic heterooctamer formed by halogen bonding between the iodonium cation and scn results of density functional theory dft calculations followed by the topological analysis of the electron density. Halogen bonding directed supramolecular quadruple and double helices from hydrogen. Halogen bonding is a type of noncovalent interaction which does not involve the formation nor breaking of actual bonds, but rather is similar to the dipoledipole interaction known as hydrogen bonding. Pdf halogen bonding in supramolecular chemistry franck. The effectiveness of xb in driving the formation of a multitude of supramolecular architectures having different and useful properties. Halogen bonding in supramolecular chemistry chemical. Despite several reports in the solid state of the supramolecular helix driven by halogen bonding,2 mimicking the natural helix in the solution phase. Imaging the halogen bond in selfassembled halogenbenzenes.
Jun 18, 2002 the term halogen bonding describes the tendency of halogen atoms to interact with lone pair possessing atoms. Towards engineering of solidstate supramolecular rotors via. Nov 17, 2014 the ability to achieve strong molecular recognition in water is a key challenge for supramolecular chemistry. Nanoscience center, department of chemistry, university of jyvaskyla, p. It is one of todays fastest growing disciplines, crossing a range of subjects from biological chemistry to materials science. Halogen bonding triggered supramolecular gel formation lorenzo meazza, jonathan a. On the importance of halogenhalogen interactions in the. In these materials, convex type halogen bonding ligands have been used as building. Halogenbondingtriggered supramolecular gel formation lorenzo meazza, jonathan a. Halogen bonding xb has drawn increased attention in the past decade as a powerful tool for crystal engineering and supramolecular chemistry 1 2 345, drug design 678, organic.
Concave halogenbonding ligands for supramolecular structure. Halogen bonding is an emerging noncovalent interaction for constructing supramolecular assemblies. The intermolecular halogen bond, hereafter the halogen bond, is an electrostatically driven, noncovalent interaction that has broad applications, including molecular selfassembly, supramolecular chemistry 2, 3, crystal engineering 4, 5, and drug design 6, 7. Towards engineering of solidstate supramolecular rotors via halogen bonding italian abstract. Halogen bonding i impact on materials chemistry and life. Halogen bonding in supramolecular chemistry, angewandte. This is due to the presence of a significant positive charge. Synergistic effects of hydrogen and halogen bonding in co. Although halogens are electronrich atoms, they act as electrophiles in these types of interactions. A halogen atom in a molecule is usually negatively charged. Halogen bonding in supramolecular chemistry metrangolo. This article is part of the 2015 supramolecular chemistry special issue. Meihui su state key laboratory of medicinal chemical biology, college of pharmacy, key laboratory of functional polymer materials of ministry of education, nankai university, tianjin, 300071 p. Some principles are presented for crystal engineering based on halogenbonding interactions.
Assuming little in the way of prior knowledge, the book covers the concepts behind the subject, its breadth, applications and the latest contemporary thinking in the area. Halogen bonding in supramolecular and solid state chemistry the article was first published on 29 sep 2017 faraday discuss. Robinson graduated from the university of stellenbosch south africa with a b. Metrangolo p1, meyer f, pilati t, resnati g, terraneo g.
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