Charge-transfer character of halogen bonding: Molecular structures and electronic spectroscopy of carbon tetrabromide and bromoform complexes with organic σ- and π-donors

Rosokha, Sergiy V.; Neretin, Ivan S.; Rosokha, Tetyana Y.; Hecht, Jürgen; Kochi, Jay K.

doi:10.1002/hc.20264

Cited by 136 publications

(144 citation statements)

References 55 publications

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“…2,10 However, more and more attention is now paid to halomethanes, which can also behave as polyfunctional XB donors. [11][12][13][14][15][16][17][18][19][20] Concurrently, halide complexes of d-metals can be employed as XB acceptors and their combination with halomethanes leads to supramolecular clusters, chains, and 3D networks. 17,18,[20][21][22] The halomethanes CBr 4 , [11][12][13][18][19][20] CHI 3 , 14,15,17,23 CHBr 3 , 11,12,20 and CFBr 3 12,19 are the most commonly used among other halomethanes in the formation of XBs with uncomplexed halides and polyhalometalate anions.…”

Section: Introductionmentioning

confidence: 99%

Diiodomethane as a halogen bond donor toward metal-bound halides

et al. 2017

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A 1, 3,5,7,3,6, chloride platinumĲII) complex (1) was obtained via the metal-mediated double coupling of 2,3-diphenylmaleimidine with both nitrile ligands in trans-Compound 1 was then co-crystallized with diiodomethane forming solvate 1·½CH 2 I 2 . The XRD experiment reveals that this solvate displays the halogen bonds H 2 C(I)-I⋯Cl-Pt and hydrogen bonds I 2 C(H)-H⋯Cl-Pt, which join two complex and one CH 2 I 2 molecules in a heterotrimeric supramolecular cluster. Inspection of the CCDC database reveals only one example of the halogen bond H 2 C(I)-I⋯I-Pt between the CH 2 I 2 molecule and metal-coordinated halide in the structure of VEMWOA. In VEMWOA, CH 2 I 2 serves solely as a halogen bond donor with no hydrogen bond contribution. Results of the Hirshfeld surface analysis and DFT calculations (M06/DZP-DKH level of theory) followed by topological analysis of the electron density distribution within the formalism of Bader's theory (QTAIM method) for both 1·½CH 2 I 2 and VEMWOA confirmed the formation of these weak interactions. The evaluated energies of halogen bonds involving CH 2 I 2 are in the 2.2-2.8 kcal mol −1 range.

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Section: Introductionmentioning

confidence: 99%

Diiodomethane as a halogen bond donor toward metal-bound halides

et al. 2017

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“…3,4 The halogen bond complex may produce a charge transfer band (CT band) in the absorption spectrum that does not belong to either component and can be used for identification of the complex, but such CT band does not always appear. 5 In the present work, through the control of the factors that affect the form of the halogen bond, it was observed that iodine can form a halogen bond with both amantadine (AMD) and amantadine hydrochloride (AMD-HCl) in chloroform and the CT bands can be clearly detected.…”

Section: Introductionmentioning

confidence: 62%

The Halogen Bond between Amantadine and Iodine and Its Application in the Determination of Amantadine Hydrochloride in Pharmaceuticals

et al. 2014

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It is proposed that molecular iodine as a donor could form halogen bonding complexes with amantadine (AMD) and amantadine hydrochloride (AMD-HCl) in chloroform and the resultant charge transfer bands (CT band) would be located at 259 and 253 nm, respectively. The halogen bonding interaction was explored by UV absorption, Raman and X-ray crystallography, and a new bonding model named N + ···N lep bond in crystal was observed. The halogen bonding complexes were utilized in the development of simple and accurate spectrophotometry for the analysis of AMD/AMD-HCl. Compared with the traditional method based on the absorption of I3 -at 290 and 365 nm, the new proposed spectrometry based on the CT band of halogen bonding complex was more sensitive and selective for the detection of AMD/AMD-HCl. Linear relationships with good correlation coefficients (>0.9994) were obtained between the absorbance and the AMD/AMD-HCl concentration in the range of 10 -180 μg mL -1 for AMD-HCl and 0.2 -13 μg mL -1 for AMD. The limit of detection (LOD) was 2.23 μg mL -1 and limit of quantification (LOQ) was 7.45 μg mL -1 for AMD-HCl. And because of the stronger bond constant between AMD and iodine than AMD-HCl, the method is more sensitive for AMD; the LOD was 0.02 μg mL -1 and LOQ was 0.08 μg mL -1 which was 100 times lower than that of AMD-HCl. Keywords

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“…Several types of monodentate, organic halogen bond donor interact favorably enough with anions to enable determinations of binding constants in organic solvent. For certain donors, changes in UV-vis spectra accompany addition of anionic acceptors, enabling spectrophotometric titrations: for example, for electron-deficient bromomethanes, anion complexation is often signaled by the appearance of a low-energy charge transfer band [26][27][28][29][30]. In the case of fluorinated donors, upfield changes in 19 F chemical shift of nearby fluorine substituents are characteristic of halogen bonding, and permit determinations of binding constants by nuclear magnetic resonance (NMR) titrations [25,31].…”

Section: Monodentate Haloorganic Donorsmentioning

confidence: 99%

Anion Recognition in Solution via Halogen Bonding

Taylor

2014

Topics in Current Chemistry

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An overview of the interactions between anions and electron-deficient, covalently bound halogens is presented. It might be anticipated that species such as halides and oxoanions would be good acceptors of halogen bonds because of their relatively high charge densities and nucleophilicities. The stabilities of the trihalide anions X3 (-) provide a clear indication that this is indeed the case. The thermodynamics of formation of the trihalides, and of analogous complexes between anions and monodentate haloorganics in organic solvent, are discussed in detail. Although the incorporation of multiple interacting groups to achieve high guest affinity has been a key principle of supramolecular chemistry for decades, it is only recently that multidentate halogen bond donors capable of anion recognition have been reported. This contribution highlights the range of architectures that have been employed as the basis for multidentate halogen bond donor design. Examples of selective and high-affinity anion recognition through halogen bonding, including implementations in polar, protic media, are discussed.

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Charge-transfer character of halogen bonding: Molecular structures and electronic spectroscopy of carbon tetrabromide and bromoform complexes with organic σ- and π-donors

Cited by 136 publications

References 55 publications

Diiodomethane as a halogen bond donor toward metal-bound halides

Diiodomethane as a halogen bond donor toward metal-bound halides

The Halogen Bond between Amantadine and Iodine and Its Application in the Determination of Amantadine Hydrochloride in Pharmaceuticals

Anion Recognition in Solution via Halogen Bonding

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