Special Issue "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: 15 April 2020.

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

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 papers will be 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. 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 2000 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 (2 papers)

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Research

Open AccessArticle
Metal–Halogen Bonding Seen through the Eyes of Vibrational Spectroscopy
Materials 2020, 13(1), 55; https://doi.org/10.3390/ma13010055 - 20 Dec 2019
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
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Open AccessArticle
Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers
Materials 2019, 12(20), 3305; https://doi.org/10.3390/ma12203305 - 11 Oct 2019
Cited by 1
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
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Planned Papers

The below list represents only planned manuscripts. Some of these manuscripts have not been received by the Editorial Office yet. Papers submitted to MDPI journals are subject to peer-review.

1. Prof. Tomislav Friščić

2. Prof. Rissanen Kari, Dr. Puttreddy Rakesh

Title: Halogen bonds in Polymeric 2,5-Dihalopyridine-Copper(I) Complexes

3. Professor Elfi Kraka

Title: Metal halogen bonding - seen through the eyes of vibrational spectroscopy

4. Prof. Peter Politzer

5. Cobaloximes as building blocks in halogen-bonded cocrystals' authored by Nikola Bedekovic, Valentina Martinez, Edi Topic, Vladimir Stilinovic and Dominik Cincic.

6. Cocrystallisation of coordination compound derived from copper(II) chloride and 4-aminoacetophenone with perhalogenated halogen bond donor' authored by Marin Liovic, Katarina Lisac and Dominik Cincic.

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