Cooperative halogen bonding and polarized π-stacking in the formation of coloured charge-transfer co-crystals

Variational energy decomposition analysis establishes charge-transfer as the origin of halogen bond strength differences that go against electrostatics.

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Fine-tuning halogen bonding properties of diiodine through halogen–halogen charge transfer – extended [Ru(2,2′-bipyridine)(CO)2X2]·I2systems (X = Cl, Br, I)

CrystEngComm ◽

10.1039/c5ce02396c ◽

2016 ◽

Vol 18 (11) ◽

pp. 1987-1995 ◽

Cited By ~ 60

Author(s):

Xin Ding ◽

Matti J. Tuikka ◽

Pipsa Hirva ◽

Vadim Yu. Kukushkin ◽

Alexander S. Novikov ◽

...

Keyword(s):

Charge Transfer ◽

Halogen Bond ◽

Ruthenium Complexes ◽

Halogen Bonding ◽

Current Paper ◽

Fine Tuning ◽

Bonding Properties

The current paper introduces the use of stable carbonyl containing ruthenium complexes, [Ru(bpy)(CO)2X2] (X = Cl, Br, I), as halogen bond acceptors for a I2halogen bond donor.

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Electron-transfer reactions of halogenated electrophiles: a different look into the nature of halogen bonding

Faraday Discussions ◽

10.1039/c7fd00074j ◽

2017 ◽

Vol 203 ◽

pp. 315-332 ◽

Cited By ~ 9

Author(s):

Sergiy V. Rosokha

Keyword(s):

Electron Transfer ◽

Charge Transfer ◽

Halogen Bond ◽

Structural Characteristics ◽

Halogen Bonding ◽

Outer Sphere ◽

Ferrocene Derivatives ◽

Dissociative Electron Transfer ◽

Covalent Interaction ◽

Electron Transfer Theory

The rates of oxidation of ferrocene derivatives by brominated molecules R-Br (CBr3CN, CBr4, CBr3NO2, CBr3COCBr3, CBr3CONH2, CBr3F, and CBr3H) were consistent with the predictions of the outer-sphere dissociative electron-transfer theory. The similar redox-reactions of the R-Br electrophiles with the typical halogen-bond acceptors tetramethyl-p-phenylenediamine (TMPD) or iodide were much faster than calculated using the same model. The fast redox-processes in these systems were related to the involvement of the transient halogen-bonded [R-Br, TMPD] or [R-Br, I−] complexes in which barriers for electron transfer were lowered by the strong electronic coupling of reactants. The Mulliken–Hush treatment of the spectral and structural characteristics of the [R-Br, TMPD] or [R-Br, I−] complexes corroborated the values of coupling elements, Hab, of 0.2–0.5 eV implied by the kinetic data. The Natural Bond Orbital analysis of these complexes indicated a noticeable donor/acceptor charge transfer, Δq, of 0.03–0.09 ē. The Hab and Δq values in the [R-Br, TMPD] and [R-Br, I−] complexes (which are similar to those in the traditional charge-transfer associates) indicate significant contribution of charge-transfer (weakly-covalent) interaction to halogen bonding. The decrease of the barrier for electron transfer between the halogen-bonded reactants demonstrated in the current work points out that halogen bonding should be taken into account in the mechanistic analysis of the reactions of halogenated species.

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Co-Crystallisation of 1,4-Diiodotetrafluorobenzene with Three Different Symmetric Dipyridylacetylacetone Isomers Produces Four Halogen-Bonded Architectures

Australian Journal of Chemistry ◽

10.1071/ch16673 ◽

2017 ◽

Vol 70 (5) ◽

pp. 594 ◽

Cited By ~ 15

Author(s):

Joshua J. Brown ◽

Aidan J. Brock ◽

Michael C. Pfrunder ◽

Julia P. Sarju ◽

Abigail Z. Perry ◽

...

Keyword(s):

Crystal Structure ◽

Hydrogen Bonding ◽

Halogen Bond ◽

Three Dimensional ◽

Halogen Bonding ◽

Supramolecular Interactions ◽

Ambient Conditions ◽

Supramolecular Architectures ◽

Crystallisation Behaviour ◽

Π Stacking

The co-crystallisation behaviour of three symmetrical dipyridylacetylacetone ligands (1,3-di(2-pyridyl)-1,3-propanedione (o-bppdH), 1,3-di(3-pyridyl)-1,3-propanedione (m-bppdH), and 1,3-di(4-pyridyl)-1,3-propanedione (p-bppdH)), with the linear halogen-bond donor 1,4-diiodotetrafluorobenzene (1,4-DITFB) has been investigated. The reaction of these components under ambient conditions in a 1 : 1 stoichiometry produced four halogen-bonded assemblies ([o-bppdH·1,4-DITFB, [m-bppdH·1,4-DITFB], [2(m-bppdH)·1,4-DITFB], and [p-bppdH·1,4-DITFB]). The combination of multiple supramolecular interactions including halogen bonding, hydrogen bonding, and π-stacking produces a range of supramolecular architectures, including one-, two-, and three-dimensional motifs. The crystal structure of m-bppdH is also reported.

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Tuning the photoelectric response of pyrene-based coordination polymers by optimizing charge transfer

Inorganic Chemistry Frontiers ◽

10.1039/d1qi00004g ◽

2021 ◽

Author(s):

Wenjuan Xu ◽

Yupei Sun ◽

Xiangru Meng ◽

Wenjing Zhang ◽

Hongwei Hou

Keyword(s):

Charge Transfer ◽

Coordination Polymers ◽

Photoelectric Response ◽

Photoelectric Properties ◽

Π Stacking

Three π–π stacked CPs were designed and synthesized for application of photoelectric response. The effect of charge transfer on the photoelectric properties is explored by adjusting the composition and π-stacking fashion of the CPs.

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Adenine as a Halogen Bond Acceptor: A Combined Experimental and DFT Study

Crystals ◽

10.3390/cryst9040224 ◽

2019 ◽

Vol 9 (4) ◽

pp. 224 ◽

Cited By ~ 7

Author(s):

Yannick Roselló ◽

Mónica Benito ◽

Elies Molins ◽

Miquel Barceló-Oliver ◽

Antonio Frontera

Keyword(s):

Density Functional ◽

Halogen Bond ◽

Lone Pair ◽

Halogen Bonding ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

Adenine Ring ◽

Bonding Interaction ◽

Donor Ability ◽

Adenine Derivative

In this work, we report the cocrystallization of N9-ethyladenine with 1,2,4,5-tetrafluoro-3,6-diiodobenzene (TFDIB), a classical XB donor. As far as our knowledge extends, this is the first cocrystal reported to date where an adenine derivative acts as a halogen bond acceptor. In the solid state, each adenine ring forms two centrosymmetric H-bonded dimers: one using N1···HA6–N6 and the other N7···HB6–N6. Therefore, only N3 is available as a halogen bond acceptor that, indeed, establishes an N···I halogen bonding interaction with TFDIB. The H-bonded dimers and halogen bonds have been investigated via DFT (Density Functional Theory) calculations and the Bader’s Quantum Theory of Atoms In Molecules (QTAIM) method at the B3LYP/6-311+G* level of theory. The influence of H-bonding interactions on the lone pair donor ability of N3 has also been analyzed using the molecular electrostatic potential (MEP) surface calculations.

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Cyclic networks of halogen-bonding interactions in molecular self-assemblies: a theoretical N—X...NversusC—X...N investigation

Acta Crystallographica Section B Structural Science Crystal Engineering and Materials ◽

10.1107/s2052520617002335 ◽

2017 ◽

Vol 73 (2) ◽

pp. 179-187

Author(s):

Ruben D. Parra ◽

Álvaro Castillo

Keyword(s):

Electron Density ◽

Self Assembly ◽

Metal Ion ◽

Halogen Atom ◽

Halogen Bond ◽

Halogen Bonding ◽

Nbo Analysis ◽

Binding Energies ◽

Cyclic Network ◽

Ability To Drive

The geometries and energetics of molecular self-assembly structures that contain a sequential network of cyclic halogen-bonding interactions are investigated theoretically. The strength of the halogen-bonding interactions is assessed by examining binding energies, electron charge transfer (NBO analysis) and electron density at halogen-bond critical points (AIM theory). Specifically, structural motifs having intramolecular N—X...N (X= Cl, Br, or I) interactions and the ability to drive molecular self-assemblyviathe same type of interactions are used to construct larger self-assemblies of up to three unit motifs. N—X...N halogen-bond cooperativity as a function of the self-assembly size, and the nature of the halogen atom is also examined. The cyclic network of the halogen-bonding interactions provides a suitable cavity rich in electron density (from the halogen atom lone pairs not involved in the halogen bonds) that can potentially bind an electron-deficient species such as a metal ion. This possibility is explored by examining the ability of the N—X...N network to bind Na+. Likewise, molecular self-assembly structures driven by the weaker C—X...N halogen-bonding interactions are investigated and the results compared with those of their N—X...N counterparts.

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Tetradentate halogen bonding macrocyclic anion receptor inspired by the “Texas-sized” molecular box

Organic & Biomolecular Chemistry ◽

10.1039/d1ob02381k ◽

2022 ◽

Author(s):

Tian Zhao ◽

Vincent Lynch ◽

Jonathan L. Sessler

Keyword(s):

Click Chemistry ◽

Halogen Bond ◽

Halogen Bonding ◽

Anion Receptor

Inspired by the tetracationic “Texas-sized” molecular box, a neutral analogue containing four iodotriazole halogen bond-promoting subunits (“Ibox”) was synthesized. This new macrocycle was prepared by means of azide-alkyne click chemistry....

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Halogen Bonding Organocatalysis Enhanced through Intramolecular Hydrogen Bonds

Chemical Communications ◽

10.1039/d1cc05475a ◽

2022 ◽

Author(s):

Asia Marie S Riel ◽

Daniel Adam Decato ◽

Jiyu Sun ◽

Orion Berryman

Keyword(s):

Hydrogen Bond ◽

Hydrogen Bonds ◽

Halogen Bond ◽

Direct Interaction ◽

Halogen Bonding ◽

Intramolecular Hydrogen Bonds ◽

Intramolecular Hydrogen

Recent results indicate a halogen bond donor is strengthened through direct interaction with a hydrogen bond to the electron-rich belt of the halogen. Here, this Hydrogen Bond enhanced Halogen Bond...

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