molecules-logo

Journal Browser

Journal Browser

Halogen Bond in Crystalline Systems

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Inorganic Chemistry".

Deadline for manuscript submissions: closed (31 December 2021) | Viewed by 14271

Special Issue Editors

Department of Biological Sciences, Webster University, St. Louis, MO 63119, USA
Interests: molecular co-crystals; solid-state organic chemistry; photoreaction in solids; thermal expansion
Rigaku Americas Corporation, The Woodlands, TX 77381, USA
Interests: X-ray crystallography; solid-state chemistry; coordination chemistry

Special Issue Information

Dear Colleagues,

Halogen bonding is a highly investigated and well-established noncovalent interaction in the formation of numerous inorganic and molecular solids. Halogen bonding continues to be an important interaction in the areas of supramolecular chemistry and crystal engineering which focuses on the design of functional materials. Halogen bonding has been exploited to control molecular recognition, photochemical behavior, and thermal expansion in molecular solids as well as the design of extended networks with novel topologies. This Special Issue aims to highlight the latest advances in halogen bonding as it applies to any and all areas of the design and formation of functional crystalline solids.

Prof. Dr. Ryan Groeneman
Dr. Eric Reinheimer
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • halogen bonding
  • supramolecular chemistry
  • crystal engineering
  • noncovalent interactions
  • molecular crystals
  • co-crystals

Published Papers (7 papers)

Order results
Result details
Select all
Export citation of selected articles as:

Research

15 pages, 8562 KiB  
Article
Complementary, Cooperative Ditopic Halogen Bonding and Electron Donor-Acceptor π-π Complexation in the Formation of Cocrystals
by Erin D. Speetzen, Chideraa I. Nwachukwu, Nathan P. Bowling and Eric Bosch
Molecules 2022, 27(5), 1527; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27051527 - 24 Feb 2022
Cited by 5 | Viewed by 1476
Abstract
This study expands and combines concepts from two of our earlier studies. One study reported the complementary halogen bonding and π-π charge transfer complexation observed between isomeric electron rich 4-N,N-dimethylaminophenylethynylpyridines and the electron poor halogen bond donor, 1-(3,5-dinitrophenylethynyl)-2,3,5,6-tetrafluoro-4-iodobenzene while [...] Read more.
This study expands and combines concepts from two of our earlier studies. One study reported the complementary halogen bonding and π-π charge transfer complexation observed between isomeric electron rich 4-N,N-dimethylaminophenylethynylpyridines and the electron poor halogen bond donor, 1-(3,5-dinitrophenylethynyl)-2,3,5,6-tetrafluoro-4-iodobenzene while the second study elaborated the ditopic halogen bonding of activated pyrimidines. Leveraging our understanding on the combination of these non-covalent interactions, we describe cocrystallization featuring ditopic halogen bonding and π-stacking. Specifically, red cocrystals are formed between the ditopic electron poor halogen bond donor 1-(3,5-dinitrophenylethynyl)-2,4,6-triflouro-3,5-diiodobenzene and each of electron rich pyrimidines 2- and 5-(4-N,N-dimethyl-aminophenylethynyl)pyrimidine. The X-ray single crystal structures of these cocrystals are described in terms of halogen bonding and electron donor-acceptor π-complexation. Computations confirm that the donor-acceptor π-stacking interactions are consistently stronger than the halogen bonding interactions and that there is cooperativity between π-stacking and halogen bonding in the crystals. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Figure 1

17 pages, 7528 KiB  
Article
Halogen-Bond Mediated [2+2] Photodimerizations: À la Carte Access to Unsymmetrical Cyclobutanes in the Solid State
by Jay Quentin, Eric W. Reinheimer and Leonard R. MacGillivray
Molecules 2022, 27(3), 1048; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27031048 - 03 Feb 2022
Cited by 2 | Viewed by 1512
Abstract
The ditopic halogen-bond (X-bond) donors 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene (1,2-, 1,3-, and 1,4-di-I-tFb, respectively) form binary cocrystals with the unsymmetrical ditopic X-bond acceptor trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (2,4-bpe). The components of each cocrystal (1,2-di-I-tFb)·(2,4-bpe), ( [...] Read more.
The ditopic halogen-bond (X-bond) donors 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene (1,2-, 1,3-, and 1,4-di-I-tFb, respectively) form binary cocrystals with the unsymmetrical ditopic X-bond acceptor trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene (2,4-bpe). The components of each cocrystal (1,2-di-I-tFb)·(2,4-bpe), (1,3-di-I-tFb)·(2,4-bpe), and (1,4-di-I-tFb)·(2,4-bpe) assemble via N···I X-bonds. For (1,2-di-I-tFb)·(2,4-bpe) and (1,3-di-I-tFb)·(2,4-bpe), the X-bond donor supports the C=C bonds of 2,4-bpe to undergo a topochemical [2+2] photodimerization in the solid state: UV-irradiation of each solid resulted in stereospecific, regiospecific, and quantitative photodimerization of 2,4-bpe to the corresponding head-to-tail (ht) or head-to-head (hh) cyclobutane photoproduct, respectively. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Figure 1

14 pages, 3410 KiB  
Article
Stimuli Responsive Materials Supported by Orthogonal Hydrogen and Halogen Bonding or I···Alkene Interaction
by Pierre Frangville, Shiv Kumar, Michel Gelbcke, Kristof Van Hecke and Franck Meyer
Molecules 2021, 26(24), 7586; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26247586 - 14 Dec 2021
Cited by 2 | Viewed by 3140
Abstract
Smart materials represent an elegant class of (macro)-molecules endowed with the ability to react to chemical/physical changes in the environment. Herein, we prepared new photo responsive azobenzenes possessing halogen bond donor groups. The X-ray structures of two molecules highlight supramolecular organizations governed by [...] Read more.
Smart materials represent an elegant class of (macro)-molecules endowed with the ability to react to chemical/physical changes in the environment. Herein, we prepared new photo responsive azobenzenes possessing halogen bond donor groups. The X-ray structures of two molecules highlight supramolecular organizations governed by unusual noncovalent bonds. In azo dye I-azo-NO2, the nitro group is engaged in orthogonal H···O···I halogen and hydrogen bonding, linking the units in parallel undulating chains. As far as compound I–azo–NH–MMA is concerned, a non-centrosymmetric pattern is formed due to a very rare I···π interaction involving the alkene group supplemented by hydrogen bonds. The Cambridge Structural Database contains only four structures showing the same I···CH2=C contact. For all compounds, an 19F-NMR spectroscopic analysis confirms the formation of halogen bonds in solution through a recognition process with chloride anion, and the reversible photo-responsiveness is demonstrated upon exposing a solution to UV light irradiation. Finally, the intermediate I–azo–NH2 also shows a pronounced color change due to pH variation. These azobenzenes are thereby attractive building blocks to design future multi-stimuli responsive materials for highly functional devices. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Graphical abstract

21 pages, 7641 KiB  
Article
Halogen Interactions in Halogenated Oxindoles: Crystallographic and Computational Investigations of Intermolecular Interactions
by Rodrigo A. Lemos Silva, Demetrio A. da Silva Filho, Megan E. Moberg, Ted M. Pappenfus and Daron E. Janzen
Molecules 2021, 26(18), 5487; https://doi.org/10.3390/molecules26185487 - 09 Sep 2021
Cited by 3 | Viewed by 1642
Abstract
X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of the interaction energy and the interaction properties were carried out for Br···Br, C-H···Br, C-H···O and N-H···O interactions. Employing Møller–Plesset second-order perturbation theory (MP2) and [...] Read more.
X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of the interaction energy and the interaction properties were carried out for Br···Br, C-H···Br, C-H···O and N-H···O interactions. Employing Møller–Plesset second-order perturbation theory (MP2) and density functional theory (DFT), the basis set superposition error (BSSE) corrected interaction energy (Eint(BSSE)) was determined using a supramolecular approach. The Eint(BSSE) results were compared with interaction energies obtained by Quantum Theory of Atoms in Molecules (QTAIM)-based methods. Reduced Density Gradient (RDG), QTAIM and Natural bond orbital (NBO) calculations provided insight into possible pathways for the intermolecular interactions examined. Comparative analysis employing the electron density at the bond critical points (BCP) and molecular electrostatic potential (MEP) showed that the interaction energies and the relative orientations of the monomers in the dimers may in part be understood in light of charge redistribution in these two compounds. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Figure 1

10 pages, 2134 KiB  
Article
Polymorphism, Halogen Bonding, and Chalcogen Bonding in the Diiodine Adducts of 1,3- and 1,4-Dithiane
by Andrew J. Peloquin, Srikar Alapati, Colin D. McMillen, Timothy W. Hanks and William T. Pennington
Molecules 2021, 26(16), 4985; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26164985 - 17 Aug 2021
Cited by 3 | Viewed by 1865
Abstract
Through variations in reaction solvent and stoichiometry, a series of S-diiodine adducts of 1,3- and 1,4-dithiane were isolated by direct reaction of the dithianes with molecular diiodine in solution. In the case of 1,3-dithiane, variations in reaction solvent yielded both the equatorial and [...] Read more.
Through variations in reaction solvent and stoichiometry, a series of S-diiodine adducts of 1,3- and 1,4-dithiane were isolated by direct reaction of the dithianes with molecular diiodine in solution. In the case of 1,3-dithiane, variations in reaction solvent yielded both the equatorial and the axial isomers of S-diiodo-1,3-dithiane, and their solution thermodynamics were further studied via DFT. Additionally, S,S’-bis(diiodo)-1,3-dithiane was also isolated. The 1:1 cocrystal, (1,4-dithiane)·(I2) was further isolated, as well as a new polymorph of S,S’-bis(diiodo)-1,4-dithiane. Each structure showed significant S···I halogen and chalcogen bonding interactions. Further, the product of the diiodine-promoted oxidative addition of acetone to 1,4-dithiane, as well as two new cocrystals of 1,4-dithiane-1,4-dioxide involving hydronium, bromide, and tribromide ions, was isolated. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Figure 1

8 pages, 1976 KiB  
Article
Chalcogen Bonding in Co-Crystals: Activation through 1,4-Perfluorophenylene vs. 4,4′-Perfluorobiphenylene Cores
by Arun Dhaka, Olivier Jeannin, Emmanuel Aubert, Enrique Espinosa and Marc Fourmigué
Molecules 2021, 26(13), 4050; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26134050 - 02 Jul 2021
Cited by 8 | Viewed by 1952
Abstract
The ability of alkylseleno/alkyltelluroacetylenes such as bis(selenomethylethynyl)-perfluorobenzene (4F-Se) to act as a ditopic chalcogen bond (ChB) donor in co-crystals with ditopic Lewis bases such as 4,4′-bipyridine is extended here to the octafluorobiphenylene analog, 4,4′-bis(selenomethylethynyl)-perfluorobiphenyl (8F-Se), with the more electron-rich [...] Read more.
The ability of alkylseleno/alkyltelluroacetylenes such as bis(selenomethylethynyl)-perfluorobenzene (4F-Se) to act as a ditopic chalcogen bond (ChB) donor in co-crystals with ditopic Lewis bases such as 4,4′-bipyridine is extended here to the octafluorobiphenylene analog, 4,4′-bis(selenomethylethynyl)-perfluorobiphenyl (8F-Se), with the more electron-rich 4,4′-bipyridylethane (bpe), showing in the 1:1 (8F-Se)•(bpe) co-crystal a shorter and more linear C−Se•••N ChB interaction than in (4F-Se)•(bpe), with Se•••N distances down to 2.958(2) Å at 150 K, i.e., a reduction ratio of 0.85 vs. the van der Waals contact distance. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Figure 1

8 pages, 27382 KiB  
Article
Controlling Topology within Halogen-Bonded Networks by Varying the Regiochemistry of the Cyclobutane-Based Nodes
by Taylor J. Dunning, Daniel K. Unruh, Eric Bosch and Ryan H. Groeneman
Molecules 2021, 26(11), 3152; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26113152 - 25 May 2021
Cited by 4 | Viewed by 1900
Abstract
The formation of a pair of extended networks sustained by halogen bonds based upon two regioisomers of a photoproduct, namely rctt-1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane (ht-PP) and rctt-1,2-bis(4-pyridyl)-3,4-bis(phenyl)cyclobutane (hh-PP), that have varied topology is reported. These networks are held together via [...] Read more.
The formation of a pair of extended networks sustained by halogen bonds based upon two regioisomers of a photoproduct, namely rctt-1,3-bis(4-pyridyl)-2,4-bis(phenyl)cyclobutane (ht-PP) and rctt-1,2-bis(4-pyridyl)-3,4-bis(phenyl)cyclobutane (hh-PP), that have varied topology is reported. These networks are held together via I⋯N halogen bonds between the photoproduct and the halogen-bond donor 1,4-diiodoperchlorobenzene (C6I2Cl4). The observed topology in each solid is controlled by the regiochemical position of the halogen-bond accepting 4-pyridyl group. This paper demonstrates the ability to vary the topology of molecular networks by altering the position of the halogen bond acceptor within the cyclobutane-based node. Full article
(This article belongs to the Special Issue Halogen Bond in Crystalline Systems)
Show Figures

Figure 1

Back to TopTop