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Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering
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Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (15 April 2020) | Viewed by 13778

Special Issue Editor

Assoc. Prof. Dominik Cinčić

E-Mail Website
Guest Editor
University of Zagreb, Faculty of Science, Department of ChemistryHorvatovac 102a, 10 000 Zagreb, Croatia
Interests: halogen bonding; mechanochemistry; supramolecular chemistry; solid-state and solvent-free synthesis of organic and metal–organic materials; crystallisation and crystallography of molecular solids

Special Issue Information

Dear Colleagues,

Halogen bonding has been recognized as one of the most important structure-directing interactions and a reliable crystal engineering tool. Halogen bonds are sigma-hole interactions that are uniquely suited for constructing functional materials by supramolecular self-assembly via a specific molecular recognition. Over the past few decades, research into halogen bonding has mostly focused on organic systems, and the use of halogen bonding to direct the assembly of metal–organic or organometallic building blocks remains unexplored. However, controlling the solid-state assembly of metal–organic units by halogen bonding, as well as other related sigma-hole interactions, is rapidly emerging as an attractive target for crystal engineering, with new potential in creating supramolecular porous materials capable of selective molecular transport or separation, sensing, or sorption. The presence of metal-based building blocks can impart halogen-bonded materials with new magnetic, optical, and electrical properties that are not readily accessible in purely organic materials. So far, a number of reported studies and approaches for incorporating metals into halogen-bonded architectures have been reported and include: (i) Single-component metal–organic solids involving coordination compounds with pendant halogen bond donor groups, (ii) multicomponent ionic structures involving ionic or neutral halogen bond donors, and (iii) metal–organic cocrystals involving neutral organic halogen bond donors.

This Special Issue will investigate this new frontier of crystal engineering and explore the recent advances in fundamental understanding, design, and applications of halogen-bonded metal–organic materials. We would be delighted to receive your original research articles, as well as reviews on the design of halogen-bonded materials involving metal-containing building blocks.

Assoc. Prof. Dominik Cinčić
Guest Editor

Manuscript Submission Information

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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. Materials 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 2600 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 bond 
  • Coordination compounds 
  • Metal–organic solids 
  • Self-assembly 
  • Cocrystals 
  • Special properties 
  • Halogen-bonded architectures 
  • Functional supramolecular materials

Published Papers (5 papers)

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Research

10 pages, 1620 KiB  
Communication
Exploring the Halogen-Bonded Cocrystallization Potential of a Metal-Organic Unit Derived from Copper(ii) Chloride and 4-Aminoacetophenone
by Vinko Nemec, Katarina Lisac, Marin Liović, Ivana Brekalo and Dominik Cinčić
Materials 2020, 13(10), 2385; https://doi.org/10.3390/ma13102385 - 22 May 2020
Cited by 6 | Viewed by 2541
Abstract
In this work, we describe a novel halogen-bonded metal-organic cocrystal involving a square-planar Cu(ii) complex and 1,4-diiodotetrafluorobenzene (14tfib) by utilizing an amine ligand whose pendant acetyl group enables halogen bonding. The cocrystal was prepared by both mechanochemical synthesis (liquid-assisted [...] Read more.
In this work, we describe a novel halogen-bonded metal-organic cocrystal involving a square-planar Cu(ii) complex and 1,4-diiodotetrafluorobenzene (14tfib) by utilizing an amine ligand whose pendant acetyl group enables halogen bonding. The cocrystal was prepared by both mechanochemical synthesis (liquid-assisted grinding) and the conventional solution-based method. Crystal structure determination by single crystal X-ray diffraction revealed that the dominant supramolecular interactions are the I···O halogen bond between 14tfib and CuCl2(aap)2 building blocks, and the N–H···Cl hydrogen bonds between CuCl2(aap)2 molecules. The combination of halogen and hydrogen bonding leads to the formation of a 2D network. Overall, this work showcases an example of the possibility for extending the complexity of metal-organic crystal structures by using halogen bonding in a way that does not affect other hydrogen bonding synthons. Full article
(This article belongs to the Special Issue Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering)
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Graphical abstract

12 pages, 2245 KiB  
Article
Cobaloximes as Building Blocks in Halogen-Bonded Cocrystals
by Nikola Bedeković, Valentina Martinez, Edi Topić, Vladimir Stilinović and Dominik Cinčić
Materials 2020, 13(10), 2370; https://doi.org/10.3390/ma13102370 - 21 May 2020
Cited by 4 | Viewed by 2543
Abstract
In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By [...] Read more.
In this work, we explore the halogen-bonded cocrystallization potential of cobaloxime complexes in the synthesis of cocrystals with perhalogenated benzenes. We demonstrate a strategy for synthesizing halogen-bonded metal–organic cocrystals by utilizing cobaloximes whose pendant bromide group and oxime oxygen enable halogen bonding. By combining three well-known halogen bond donor molecules differing in binding geometry and composition with three cobaloxime units, we obtained a total of four previously unreported cocrystals. Single crystal X-ray diffraction experiments showed that the majority of obtained cocrystals exhibited the formation of the targeted I···O and I···Br motives. These results illustrate the potential of cobaloximes as halogen bond acceptors and indicate that this type of halogen bond acceptors may offer a novel route to metal–organic halogen-bonded cocrystals. Full article
(This article belongs to the Special Issue Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering)
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Graphical abstract

15 pages, 4593 KiB  
Article
Hydrogen vs. Halogen Bonds in 1-Halo-Closo-Carboranes
by Ibon Alkorta, Jose Elguero and Josep M. Oliva-Enrich
Materials 2020, 13(9), 2163; https://doi.org/10.3390/ma13092163 - 7 May 2020
Cited by 10 | Viewed by 2657
Abstract
A theoretical study of the hydrogen bond (HB) and halogen bond (XB) complexes between 1-halo-closo-carboranes and hydrogen cyanide (NCH) as HB and XB probe has been carried out at the MP2 computational level. The energy results show that the HB complexes [...] Read more.
A theoretical study of the hydrogen bond (HB) and halogen bond (XB) complexes between 1-halo-closo-carboranes and hydrogen cyanide (NCH) as HB and XB probe has been carried out at the MP2 computational level. The energy results show that the HB complexes are more stable than the XBs for the same system, with the exception of the isoenergetic iodine derivatives. The analysis of the electron density with the quantum theory of atoms in molecules (QTAIM) shows the presence of a unique intermolecular bond critical point with the typical features of weak noncovalent interactions (small values of the electron density and positive Laplacian and total energy density). The natural energy decomposition analysis (NEDA) of the complexes shows that the HB and XB complexes are dominated by the charge-transfer and polarization terms, respectively. The work has been complemented with a search in the CSD database of analogous complexes and the comparison of the results, with those of the 1-halobenzene:NCH complexes showing smaller binding energies and larger intermolecular distances as compared to the 1-halo-closo-carboranes:NCH complexes. Full article
(This article belongs to the Special Issue Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering)
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23 pages, 10673 KiB  
Article
Metal–Halogen Bonding Seen through the Eyes of Vibrational Spectroscopy
by Vytor P. Oliveira, Bruna L. Marcial, Francisco B. C. Machado and Elfi Kraka
Materials 2020, 13(1), 55; https://doi.org/10.3390/ma13010055 - 20 Dec 2019
Cited by 27 | Viewed by 3178
Abstract
Incorporation of a metal center into halogen-bonded materials can efficiently fine-tune the strength of the halogen bonds and introduce new electronic functionalities. The metal atom can adopt two possible roles: serving as halogen acceptor or polarizing the halogen donor and acceptor groups. We [...] Read more.
Incorporation of a metal center into halogen-bonded materials can efficiently fine-tune the strength of the halogen bonds and introduce new electronic functionalities. The metal atom can adopt two possible roles: serving as halogen acceptor or polarizing the halogen donor and acceptor groups. We investigated both scenarios for 23 metal–halogen dimers trans-M(Y2)(NC5H4X-3)2 with M = Pd(II), Pt(II); Y = F, Cl, Br; X = Cl, Br, I; and NC5H4X-3 = 3-halopyridine. As a new tool for the quantitative assessment of metal–halogen bonding, we introduced our local vibrational mode analysis, complemented by energy and electron density analyses and electrostatic potential studies at the density functional theory (DFT) and coupled-cluster single, double, and perturbative triple excitations (CCSD(T)) levels of theory. We could for the first time quantify the various attractive contacts and their contribution to the dimer stability and clarify the special role of halogen bonding in these systems. The largest contribution to the stability of the dimers is either due to halogen bonding or nonspecific interactions. Hydrogen bonding plays only a secondary role. The metal can only act as halogen acceptor when the monomer adopts a (quasi-)planar geometry. The best strategy to accomplish this is to substitute the halo-pyridine ring with a halo-diazole ring, which considerably strengthens halogen bonding. Our findings based on the local mode analysis provide a solid platform for fine-tuning of existing and for design of new metal–halogen-bonded materials. Full article
(This article belongs to the Special Issue Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering)
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Graphical abstract

11 pages, 7451 KiB  
Article
Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
by Carolina von Essen, Kari Rissanen and Rakesh Puttreddy
Materials 2019, 12(20), 3305; https://doi.org/10.3390/ma12203305 - 11 Oct 2019
Cited by 9 | Viewed by 2457
Abstract
Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A–Cu and C5−X5···A–Cu halogen bonds. The reaction of the [...] Read more.
Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2−X2···A–Cu and C5−X5···A–Cu halogen bonds. The reaction of the 2,5-dihalopyridines and Cu(I) salts allows the synthesis of eight 1-D coordination polymers and a discrete structure. The resulting Cu(I)-complexes are linked by C−X···A–Cu halogen bonds forming 3-D supramolecular networks. The C−X···A–Cu halogen bonds formed between halopyridine ligands and copper(I)-bound halide ions are stronger than C−X···X’–C interactions between two 2,5-dihalopyridine ligands. The C5−I5···I–Cu and C5−Br5···Br–Cu halogens bonds are shorter for C2-fluorine than C2-chlorine due to the greater electron-withdrawing power of fluorine. In 2,5-diiodopyridine-Cu(I)Br complex, the shorter C2−I2···Br–Cu [3.473(5) Å] distances are due to the combined polarization of C2-iodine by C2−I2···Cu interactions and para-electronic effects offered by the C5-iodine, whilst the long halogen bond contacts for C5−I5···Br–Cu [3.537(5) Å] are indicative that C2-iodine has a less para-electronic influence on the C5-iodine. In 2-fluoro-5-X-pyridine-Cu(I) complexes, the C2-fluorine is halogen bond passive, while the other C2-halogens in 2,5-dihalopyridine-Cu(I), including C2-chlorine, participate in halogen bonding interactions. Full article
(This article belongs to the Special Issue Metal-Containing Halogen-Bonded Materials: A New Frontier of Halogen-Bonded Crystal Engineering)
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