Synthesis of binaphthyl-based push-pull chromophores with supramolecularly polarizable acceptor ends

We report on the design and synthesis of new enantiopure binaphthyl derivatives in which electron-donating and electron-withdrawing substituents are placed in direct conjugation, to create push-pull dyes potentially active for NLO applications. The dyes, unprecedentedly, extend their π-bridge from the 3,3′ positions of the binaphthyl units and incorporate as acceptors 1,3-dicarbonyl and tetrafluorobenzene units, useful for further supramolecular polarization of the chiral dyes

Halogen and hydrogen bonding in multicomponent crystals of tetrabromo-1H-benzotriazole

4,5,6,7-Tetrabromo-1H-benzotriazole (TBBT) is still considered a reference inhibitor of casein kinase II (CK2), a valuable target for anticancer therapy, even though the poor solubility in water of this active pharmaceutical ingredient (API) has prevented its implementation in therapy. We decided to explore the interactions preferentially formed by TBBT in crystalline solids in order to obtain information helpful for the development of new TBBT cocrystals possibly endowed with improved bioavailability. In this paper, we describe the synthesis and the structural characterization of the TBBT methanol solvate and of the TBBT salt with N,N,Nâ\u80²,Nâ\u80²-tetramethylethylenediamine. It is shown that TBBT can give rise to several competing interactions. This API is clearly a good halogen bond (XB) donor, with bromine atoms adjacent to the triazole ring possibly better donors than the two others. TBBT is also a good hydrogen bond (HB) donor, with the triazole hydrogen forming an HB with the acceptor or being transferred to it. Interestingly, one of the triazole nitrogens was proven to be able to work as a hydrogen bond acceptor

From molecules to materials : Engineering new ionic liquid crystals through halogen bonding

Herein, we demonstrate that a bottom-up approach, based on halogen bonding (XB), can be successfully applied for the design of a new type of ionic liquid crystals (ILCs). Taking advantages of the high specificity of XB for haloperfluorocarbons and the ability of anions to act as XB-acceptors, we obtained supramolecular complexes based on 1-alkyl-3-methylimidazolium iodides and iodoperfluorocarbons, overcoming the well-known immiscibility between hydrocarbons (HCs) and perfluorocarbons (PFCs). The high directionality of the XB combined with the fluorophobic effect, allowed us to obtain enantiotropic liquid crystals where a rigid, non-aromatic, XB supramolecular anion acts as mesogenic core. X-ray structure analysis of the complex between 1-ethyl-3-methylimidazolium iodide and iodoperfluorooctane showed the presence of a layered structure, which is a manifestation of the well-known tendency to segregation of perfluoroalkyl chains. This is consistent with the observation of smectic mesophases. Moreover, all the reported complexes melt below 100 °C, and most are mesomorphic even at room temperature, despite that the starting materials were non-mesomorphic in nature. The supramolecular strategy reported here provides new design principles for mesogen design allowing a totally new class of functional materials

Coordination networks incorporating halogen-bond donor sites and azobenzene groups

Two Zn coordination networks, {[Zn(1)(Py)(2)](2)(2-propanol)}(n) (3) and {[Zn(1)(2)(Bipy)(2)](DMF)(2)}(n) (4), incorporating halogen-bond (XB) donor sites and azobenzene groups have been synthesized and fully characterized. Obtaining 3 and 4 confirms that it is possible to use a ligand wherein its coordination bond acceptor sites and XB donor sites are on the same molecular scaffold (i.e., an aromatic ring) without interfering with each other. We demonstrate that XBs play a fundamental role in the architectures and properties of the obtained coordination networks. In 3, XBs promote the formation of 2D supramolecular layers, which, by overlapping each other, allow the incorporation of 2-propanol as a guest molecule. In 4, XBs support the connection of the layers and are essential to firmly pin DMF solvent molecules through I center dot center dot center dot O contacts, thus increasing the stability of the solvated systems

C–halogen…O supramolecular synthons:in situcryocrystallisation of 1,2-dihalotetrafluoroethane/HMPA adducts

The in situ cryocrystallisation technique has been used to obtain four adducts between hexamethylphosphortriamide and 1,2-dihalotetrafluoroethanes having iodine, bromine and chlorine as halogen-bonding donor atoms. These systems allowed for a precise comparison of different C-X···O synthons. The effectiveness and reliability of the pharmacologically important C-Cl···O synthons are proven. © 2013 Copyright Taylor and Francis Group, LLC

Synthesis of pyrrole derivatives of serinol for functionalization of carbon allotropes

N-Pyrrole-based heterocycles are present in many natural products,[1] medicinal agents,[2] and functional materials,[3,4] therefore substantial attention has been paid to develop efficient methods for pyrroles synthesis. Moreover, they are precursors for the synthesis of poly N-alkyl pyrroles which have wide ranging applications in electronics and sensors due to their tunable optoelectronic properties. We present here one operationally simple, practical and economical Paal-Knorr pyrrole condensation of serinol (2-amino-propan-1,3-diol, 1) with beta-dicarbonyl compounds 2 (and related acetal/ketals or enolesters), under neat conditions in the absence of any catalysts, which allows the synthesis of N-serinopyrrole derivatives (3) in good to excellent yield. Depending on substituents, compounds 3 show quite interesting amphiphilic polar/unpolar and variable -interaction properties. The mechanistic conclusion reached in the study, allowed to identify a direct method for the preparation of the precursor serinol-pyrrole from sugar derivatives. Typical examples of this reaction is the dehydrative condensation of galactaric acid (4) with serinol (1) (i.e. its serinol salt or other derivatives). Methods for the derivatization of carbon allotropes (CNT, Graphenes and Carbon Black) by the prepared pyrroles were investigated and the good dispersion properties of the resulting material proved

Dimensional caging of polyiodides: cation-templated synthesis using bipyridinium salts

none8The potential of bipyridinium derivatives in the cation templated synthesis of polyiodides has been explored by applying the strategy of size-matching between cations and anions. Bipyridinium cations 1-4, bearing benzyl and functionalized benzyl pendants at nitrogen atoms, are able to template the selective formation of I(4)(2-) and I(3)(-) species. Thanks to the supramolecular space compartmentation induced by the benzyl pendants, the formation of I(4)(2-) and I(3)(-) is independent of the stoichiometry adopted in the crystallization procedure. Bipyridinium cation 5, bearing methyl pendants, is unable to induce space compartmentation and different polyiodides are obtained depending on the stoichiometry used in the crystallization process as the cation-anion size-matching alone does not control the polyiodide formation.M. D. Garcia; J. Marti-Rujas; P. Metrangolo; C. Peinador; T. Pilati; G. Resnati; G. Terraneo; M. UrsiniGarcia, M. D.; Marti Rujas, J.; Metrangolo, Pierangelo; Peinador, C.; Pilati, TULLIO MARIA; Resnati, Giuseppe; Terraneo, Giancarlo; Ursini, Maurizi

Halogen bond directionality translates tecton geometry into self-assembled architecture geometry

The structures of halogen-bonded infinite chains involving two diiodoperfluoroalkanes and a bent bis(pyrid-4′-yl)oxadiazole show that the geometry of the pyridyl pendant rings is translated into the angle between the formed halogen bonds. © 2013 The Royal Society of Chemistry

The Halogen Bond

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design

Structural characterization of new fluorinated mesogens obtained through halogen-bond driven self-assembly

We describe the synthesis and characterization of new trimeric complexes obtained upon halogen-bond driven self-assembly of 1,4-diiodotetrafluorobenzene or α,ω- diiodoperfluoroalkanes, acting as XB-donors, with an alkoxystilbazole derivative functionalized with a methacrylate terminal group, acting as XB-acceptor. Despite the fact that the starting materials are not mesomorphic in nature, the obtained halogen-bonded complexes exhibit monotropic LC behaviour with smectic A phases possibly resulting from segregation between fluorocarbon and hydrocarbon chains. The obtained supramolecular mesogens possess reactive groups suitable for incorporation into liquid crystalline elastomeric actuators