Halogen Bonded Supramolecular Assemblies of [Ru(bipy)(CN)4]2− Anions and N-Methyl-Halopyridinium Cations in the Solid State and in Solution

Derossi, Sofia; Brammer, Lee; Hunter, Christopher A.; Ward, Michael D.

doi:10.1021/ic8021529

Cited by 88 publications

(65 citation statements)

References 70 publications

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“…Among different noncovalent interactions, the halogen bond (X-bond) attracts particular attention of researchers because, similarly as the hydrogen bond (H-bond), it is responsible for physical, chemical, and biologic properties of a large group of chemical species [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. The X-bond is of the strength close to that of H-bond [1] and is strongly directional [17].…”

Section: Introductionmentioning

confidence: 99%

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

Bankiewicz

Palusiak

2012

Struct Chem

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A search through Crystal Structure Database was performed and the distances in contacts of XÁÁÁN,O, XÁÁÁH(N,O), and XÁÁÁC type were collected together with the information on spatial arrangement of the interacting fragments. A detailed statistical analysis showed that the shape of the halogen atom cannot be simply concluded on the basis of interatomic distances in crystal state although originally the concept of anisotropic charge distribution around halogen nuclei was postulated on the basis of such an analysis. It was proven that the conclusions in that case strongly depend on the type of center interacting with the halogen atom. Therefore, it was postulated that the shape of the halogen atom can be estimated for the unperturbed (due to intermolecular interactions) halogen atom. For this purpose, a method was provided to make possible a numerical quantification of the anisotropy of the halogen atom on the basis of electron density measurements performed within the framework of Atoms in Molecules Quantum Theory. The anisotropy of Cl and Br atoms in H 3 C-X and F 3 C-X (X=Cl, Br) was estimated for MP2 and DFT-B3LYP methods and several different basis sets. The influence of the method and the basis set on the degree of anisotropic distribution of electron density around halogen nuclei was discussed.Keywords Halogen bond Á The shape of the atom Á QTAIM Á DFT Á MP2 Á Basis set

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Section: Introductionmentioning

confidence: 99%

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

Bankiewicz

Palusiak

2012

Struct Chem

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“…The ability of halometallates [38][39][40] (as well as cyano [41,42] and thiocyanato [19] analogs) to act as halogen bond acceptors has been extensively explored [43], particularly by Brammer et al, and several series of salts with halo-pyridinium cations as halogen bond donors were reported. Neutral halopyridines (Fig.…”

Section: Halopyridine Complexes Of Metal Halidesmentioning

confidence: 99%

Organizing Radical Species in the Solid State with Halogen Bonding

Fourmigué

Lieffrig

2014

Topics in Current Chemistry

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The electronic properties (conductivity, magnetism) of radical systems in the solid state essentially depend on (1) the extent of delocalization of the spin density in the molecule and (2) the intermolecular interactions between radicals. The halogen bond has proven very efficient in engineering such magnetic or conducting structures and recent advances along these lines are reviewed here. Three situations are considered: (1) halogenated radical species acting as halogen bond donors, as found in iodotetrathiafulvalene-based chiral conductors or bilayer systems, and in spin crossover (SCO) complexes with halogenated ligands, (2) radical species acting as halogen bond acceptors, such as neutral nitronyl species or anionic, mixed-valence dithiolene complexes, interacting with closed-shell halogen bond donors (iodoperfluoro alkanes and arenes, iodo- or bromo-pyridinium cations), and, finally, (3) charge transfer salts where both halogen bond donor and acceptor are radical species.

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“…Nevertheless, the effectiveness of halogen bonds are not restricted to the use of haloperfluorocarbons; activation of the halogens can also be achieved by other means, such as sp hybridization of the carbon atom attached to the halogen or use of positively charged molecules, leading to novel materials with interesting properties. Examples of these include structural control of polyoxometallates [39], polymerization [40], or design of conducting [41], magnetic [42], and luminescent [43] molecular materials. Functionalization of porous materials with substituents capable of halogen bonding is an interesting feature that can lead to many applications, although competition with the formation of the network has yet to be overcome [44].…”

Section: Halogens As Electrophilesmentioning

confidence: 99%

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

Espallargas

2010

Ideas in Chemistry and Molecular Sciences

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The ultimate goal of a solid-state chemist is the rational design and synthesis of crystalline materials with the presence of specific and tunable chemical or physical properties, the so-called ''smart materials.'' Porosity, magnetism, chirality, conductivity, superconductivity, spin-transition, optical, and photophysical properties can be exploited for a wide variety of applications including gas storage, separations, electronic, catalysis, nonlinear optics, or drug delivery, and are therefore the objectives of intense research activity. The occurrence of these properties in crystalline materials 1) results from the combination of two aspects: (i) the molecular units (building blocks) that compose the crystal and (ii) the arrangement of these building blocks in the crystal. Controlling the former is relatively simple, and essentially it is only limited to the imagination and creativity of the researcher, since molecular chemistry has, over about two centuries, developed a wide range of very powerful procedures for creating even more sophisticated molecules from atoms linked by covalent bonds. On the contrary, organizing the molecules, or building blocks, in a predetermined manner is difficult to accomplish given that the structure of crystalline solids results from a delicate balance between all the intermolecular interactions present in the crystal, maximizing the attractive ones and minimizing the repulsive ones while, although not always, adopting the densest packing [1]. When a single strong interaction dominates in the system other weak intermolecular interactions normally play a secondary role in the crystal packing, providing support to the stronger interactions. In this situation, control over the molecular packing can successfully be achieved [2], although the presence of numerous weak interactions can in some cases overwhelm much stronger interactions as a result of their abundance [3]. Further difficulties can be encountered if the building blocks are 1) It should of course be acknowledged that crystalline products might not always represent the most desirable form of a material with respect to a given application.

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Halogen Bonded Supramolecular Assemblies of [Ru(bipy)(CN)₄]²⁻ Anions and N-Methyl-Halopyridinium Cations in the Solid State and in Solution

Cited by 88 publications

References 70 publications

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

The shape of the halogen atom—anisotropy of electron distribution and its dependence on basis set and method used

Organizing Radical Species in the Solid State with Halogen Bonding

Supramolecular Interactions and Smart Materials: C–X…X′–M Halogen Bonds and Gas Sorption in Molecular Solids

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