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Inorganics
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Recent Progress in Coordination Chemistry
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Recent Progress in Coordination Chemistry

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Coordination Chemistry".

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 18007

Printed Edition Available!
A printed edition of this Special Issue is available here.

Special Issue Editors

Prof. Dr. Peter Segľa

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Guest Editor
Institute of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic
Interests: infrared spectroscopy; transition metal chemistry; copper and cobalt complexes
Special Issues, Collections and Topics in MDPI journals
Dr. Ján Pavlik

E-Mail Website
Guest Editor
Department of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, 81237 Bratislava, Slovak Republic
Interests: computational chemistry; spin crossover; single molecule magnets
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Synergy is at the heart of new discoveries, and it always appears at the contact area between scientific disciplines. In this regard, we have always been fascinated by coordination chemistry, which has been synergistic by itself since its inception and unites contrasting fields, such as quantum chemistry, material design, and medicine, to name only a few. Sixty years ago, the same passion inspired our past colleague, Prof. Ján Gažo, in setting up the Conference on Coordination and Bioinorganic Chemistry, as the only scientific event in the field, being held regularly at the same place (Castle of Smolenice, Slovakia). As the number of participants is limited due to various reasons, not to mention the layout of the castle, we are pleased to extend this tradition into the electronic space. Therefore, we invite you to share your novel ideas and achievements in coordination chemistry by contributing original papers and reviews to this Special Issue of Inorganics.

Prof. Dr. Peter Segľa
Dr. Ján Pavlik
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. Inorganics is an international peer-reviewed open access monthly 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.

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Published Papers (11 papers)

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Editorial

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3 pages, 1501 KiB  
Editorial
Recent Progress in Coordination Chemistry
by Peter Segľa and Ján Pavlik
Inorganics 2023, 11(6), 250; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics11060250 - 08 Jun 2023
Cited by 1 | Viewed by 880
Abstract
The following Special Issue of Inorganics is based on the discussions initiated at the International Conference on Coordination and Bioinorganic Chemistry (ICCBIC), which has been organized and held biennially since 1964 [...] Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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Research

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29 pages, 8462 KiB  
Article
Structural and Biological Properties of Heteroligand Copper Complexes with Diethylnicotinamide and Various Fenamates: Preparation, Structure, Spectral Properties and Hirshfeld Surface Analysis
by Milan Piroš, Martin Schoeller, Katarína Koňariková, Jindra Valentová, Ľubomír Švorc, Ján Moncoľ, Marian Valko and Jozef Švorec
Inorganics 2023, 11(3), 108; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics11030108 - 06 Mar 2023
Cited by 9 | Viewed by 1805
Abstract
Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of [...] Read more.
Herein, we discuss the synthesis, structural and spectroscopic characterization, and biological activity of five heteroligand copper(II) complexes with diethylnicotinamide and various fenamates, as follows: flufenamate (fluf), niflumate (nifl), tolfenamate (tolf), clonixinate (clon), mefenamate (mef) and N, N-diethylnicotinamide (dena). The complexes of composition: [Cu(fluf)2(dena)2(H2O)2] (1), [Cu(nifl)2(dena)2] (2), [Cu(tolf)2(dena)2(H2O)2] (3), [Cu(clon)2(dena)2] (4) and [Cu(mef)2(dena)2(H2O)2] (5), were synthesized, structurally (single-crystal X-ray diffraction) and spectroscopically characterized (IR, EA, UV-Vis and EPR). The studied complexes are monomeric, forming a distorted tetragonal bipyramidal stereochemistry around the central copper ion. The crystal structures of all five complexes were determined and refined with an aspheric model using the Hirshfeld atom refinement method. Hirshfeld surface analysis and fingerprint plots were used to investigate the intermolecular interactions in the crystalline state. The redox properties of the complexes were studied and evaluated via cyclic voltammetry. The complexes exhibited good superoxide scavenging activity as determined by an NBT assay along with a copper-based redox-cycling mechanism, resulting in the formation of ROS, which, in turn, predisposed the studied complexes for their anticancer activity. The ability of complexes 1–4 to interact with calf thymus DNA was investigated using absorption titrations, viscosity measurements and an ethidium-bromide-displacement-fluorescence-based method, suggesting mainly the intercalative binding of the complexes to DNA. The affinity of complexes 1–4 for bovine serum albumin was determined via fluorescence emission spectroscopy and was quantitatively characterized with the corresponding binding constants. The cytotoxic properties of complexes 1–4 were studied using the cancer cell lines A549, MCF-7 and U-118MG, as well as healthy MRC-5 cells. Complex 4 exhibited moderate anticancer activity on the MCF-7 cancer cells with IC50 = 57 μM. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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19 pages, 6775 KiB  
Article
Coordination Chemistry of Polynitriles, Part XII—Serendipitous Synthesis of the Octacyanofulvalenediide Dianion and Study of Its Coordination Chemistry with K+ and Ag+
by Patrick Nimax, Yannick Kunzelmann and Karlheinz Sünkel
Inorganics 2023, 11(2), 71; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics11020071 - 02 Feb 2023
Cited by 1 | Viewed by 1185
Abstract
The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] ( [...] Read more.
The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] (5), which can be transformed via reaction with AgNO3 to the corresponding Ag+ salt (4), which in turn can be reacted with KCl to yield the corresponding K+ salt 6. The molecular and crystal structures of 4–6 could be determined, and show a significantly twisted aromatic dianion which uses all its nitrile groups for coordination to the metals; 4 and 6 form three-dimensional coordination polymers with fourfold coordinated Ag+ and eightfold coordinated K+ cations. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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18 pages, 3303 KiB  
Article
Interactions of an Artificial Zinc Finger Protein with Cd(II) and Hg(II): Competition and Metal and DNA Binding
by Bálint Hajdu, Éva Hunyadi-Gulyás and Béla Gyurcsik
Inorganics 2023, 11(2), 64; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics11020064 - 29 Jan 2023
Cited by 2 | Viewed by 1939
Abstract
Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as [...] Read more.
Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as Cd(II) or Hg(II) might be especially dangerous because of their similar chemical properties to Zn(II). Most competition studies carried out so far have involved small zinc finger peptides. Therefore, we have investigated the interactions of toxic metal ions with a zinc finger proteins consisting of three finger units and the consequences on the DNA binding properties of the protein. Binding of one Cd(II) per finger subunit of the protein was shown by circular dichroism spectroscopy, fluorimetry and electrospray ionisation mass spectrometry. Cd(II) stabilised a similar secondary structure to that of the Zn(II)-bound protein but with a slightly lower affinity. In contrast, Hg(II) could displace Zn(II) quantitatively (logβ′ ≥ 16.7), demolishing the secondary structure, and further Hg(II) binding was also observed. Based on electrophoretic gel mobility shift assays, the Cd(II)-bound zinc finger protein could recognise the specific DNA target sequence similarly to the Zn(II)-loaded form but with a ~0.6 log units lower stability constant, while Hg(II) could destroy DNA binding completely. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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24 pages, 6449 KiB  
Article
Low-Dimensional Compounds Containing Bioactive Ligands. Part XX: Crystal Structures, Cytotoxic, Antimicrobial Activities and DNA/BSA Binding of Oligonuclear Zinc Complexes with Halogen Derivatives of 8-Hydroxyquinoline
by Michaela Harmošová, Martin Kello, Michal Goga, Ľudmila Tkáčiková, Mária Vilková, Danica Sabolová, Simona Sovová, Erika Samoľová, Miroslava Litecká, Veronika Kuchárová, Juraj Kuchár and Ivan Potočňák
Inorganics 2023, 11(2), 60; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics11020060 - 26 Jan 2023
Cited by 4 | Viewed by 1390
Abstract
Two tetranuclear [Zn4Cl2(ClQ)6]·2DMF (1) and [Zn4Cl2(ClQ)6(H2O)2]·4DMF (2), as well as three dinuclear [Zn2(ClQ)3(HClQ)3]I3 (3), [...] Read more.
Two tetranuclear [Zn4Cl2(ClQ)6]·2DMF (1) and [Zn4Cl2(ClQ)6(H2O)2]·4DMF (2), as well as three dinuclear [Zn2(ClQ)3(HClQ)3]I3 (3), [Zn2(dClQ)2(H2O)6(SO4)] (4) and [Zn2(dBrQ)2(H2O)6(SO4)] (5), complexes (HClQ = 5-chloro-8-hydroxyquinoline, HdClQ = 5,7-dichloro-8-hydroxyquinoline and HdBrQ = 5,7-dibromo-8-hydroxyquinoline) were prepared as possible anticancer or antimicrobial agents and characterized by IR spectroscopy, elemental analysis and single crystal X-ray structure analysis. The stability of the complexes in solution was verified by NMR spectroscopy. Antiproliferative activity and selectivity of the prepared complexes were studied using in vitro MTT assay against the HeLa, A549, MCF-7, MDA-MB-231, HCT116 and Caco-2 cancer cell lines and on the Cos-7 non-cancerous cell line. The most sensitive to the tested complexes was Caco-2 cell line. Among the tested complexes, complex 3 showed the highest cytotoxicity against all cell lines. Unfortunately, all complexes showed only poor selectivity to normal cells, except for complex 5, which showed a certain level of selectivity. Antibacterial potential was observed for complex 5 only. Moreover, the DNA/BSA binding potential of complexes 1–3 was investigated by UV-vis and fluorescence spectroscopic methods. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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12 pages, 2648 KiB  
Article
Reaching the Maximal Unquenched Orbital Angular Momentum L = 3 in Mononuclear Transition-Metal Complexes: Where, When and How?
by Vladimir S. Mironov
Inorganics 2022, 10(12), 227; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10120227 - 27 Nov 2022
Cited by 4 | Viewed by 1699
Abstract
The conditions for achieving the maximal unquenched orbital angular momentum L = 3 and the highest magnetic anisotropy in mononuclear 3d complexes with axial coordination symmetry are examined in terms of the ligand field theory. It is shown that, apart from the known [...] Read more.
The conditions for achieving the maximal unquenched orbital angular momentum L = 3 and the highest magnetic anisotropy in mononuclear 3d complexes with axial coordination symmetry are examined in terms of the ligand field theory. It is shown that, apart from the known linear two-coordinate 3d7 complex CoII(C(SiMe2ONaph)3)2 characterized by record magnetic anisotropy and single-molecule magnet (SMM) performance (with the largest known spin-reversal barrier Ueff = 450 cm−1), the maximal orbital angular momentum L = 3 can also be obtained in linear two-coordinate 3d2 complexes (V3+, Cr4+) and in trigonal-prismatic 3d3 (Cr3+, Mn4+) and 3d8 (Co+, Ni2+) complexes. A comparative assessment of the SMM performance of the 3d2, 3d3 and 3d8 complexes indicates that they are unlikely to compete with the record linear complex CoII(C(SiMe2ONaph)3)2, whose magnetic anisotropy is close to the physical limit for a 3d metal. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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17 pages, 2202 KiB  
Article
Low-Dimensional Compounds Containing Bioactive Ligands. Part XIX: Crystal Structures and Biological Properties of Copper Complexes with Halogen and Nitro Derivatives of 8-Hydroxyquinoline
by Martina Kepeňová, Martin Kello, Romana Smolková, Michal Goga, Richard Frenák, Ľudmila Tkáčiková, Miroslava Litecká, Jan Šubrt and Ivan Potočňák
Inorganics 2022, 10(12), 223; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10120223 - 25 Nov 2022
Cited by 2 | Viewed by 1170
Abstract
Six new copper(II) complexes were prepared: [Cu(ClBrQ)2] (1a, 1b), [Cu(ClBrQ)2]·1/2 diox (2) (diox = 1,4-dioxane), [Cu(BrQ)2] (3), [Cu(dNQ)2] (4), [Cu(dNQ)2(DMF)2] (5 [...] Read more.
Six new copper(II) complexes were prepared: [Cu(ClBrQ)2] (1a, 1b), [Cu(ClBrQ)2]·1/2 diox (2) (diox = 1,4-dioxane), [Cu(BrQ)2] (3), [Cu(dNQ)2] (4), [Cu(dNQ)2(DMF)2] (5) and [Cu(ClNQ)2] (6), where HClBrQ is 5-chloro-7-bromo-8-hydroxyquinoline, HBrQ is 7-bromo-8-hydroxyquinoline, HClNQ is 5-chloro-7-nitro-8-hydroxyquinoline and HdNQ is 5,7-dinitro-8-hydroxyquinoline. Prepared compounds were characterised by infrared spectroscopy, elemental analysis and by X-ray structural analysis. Structural analysis revealed that all complexes are molecular. Square planar coordination of copper atoms in [Cu(XQ)2] (XQ = ClBrQ (1a, 1b), BrQ (3) and ClNQ (6)) and tetragonal bipyramidal coordination in [Cu(dNQ)2(DMF)2] (5) complexes were observed. In these four complexes, bidentate chelate coordination of XQ ligands via oxygen and nitrogen atoms was found. Hydrogen bonds stabilizing the structure were observed in [Cu(dNQ)2(DMF)2] (5) and [Cu(ClNQ)2] (6), no other nonbonding interactions were noticed in all five structures. The stability of the complexes in DMSO and DMSO/water was evaluated by UV-Vis spectroscopy. Cytotoxic activity of the complexes and ligands was tested against MCF-7, MDA-MB-231, HCT116, CaCo2, HeLa, A549 and Jurkat cancer cell lines. The selectivity of the complexes was verified on a noncancerous Cos-7 cell line. Antiproliferative activity of the prepared complexes was very low in comparison with cisplatin, except complex 3; however, its activity was not selective and was similar to the activity of its ligand HBrQ. Antibacterial potential was observed only with ligand HClNQ. Radical scavenging experiments revealed relatively high antioxidant activity of complex 3 against ABTS radical. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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18 pages, 2154 KiB  
Article
The Role of the Bridge in Single-Ion Magnet Behaviour: Reinvestigation of Cobalt(II) Succinate and Fumarate Coordination Polymers with Nicotinamide
by Marek Brezovan, Jana Juráková, Ján Moncol, Ľubor Dlháň, Maria Korabik, Ivan Šalitroš, Ján Pavlik and Peter Segľa
Inorganics 2022, 10(9), 128; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10090128 - 30 Aug 2022
Cited by 3 | Viewed by 1756
Abstract
Two previously synthesized cobalt(II) coordination polymers; {[Co(μ2-suc)(nia)2(H2O)2]·2H2O}n (suc = succinate(2−), nia = nicotinamide) and [Co(μ2-fum)(nia)2(H2O)2]n (fum = fumarate(2−)) were prepared and [...] Read more.
Two previously synthesized cobalt(II) coordination polymers; {[Co(μ2-suc)(nia)2(H2O)2]·2H2O}n (suc = succinate(2−), nia = nicotinamide) and [Co(μ2-fum)(nia)2(H2O)2]n (fum = fumarate(2−)) were prepared and thoroughly characterized. Both complexes form 1D coordination chains by bonding of Co(nia)2(H2O)2 units through succinate or fumarate ligands while these chains are further linked through hydrogen bonds to 3D supramolecular networks. The intermolecular interactions of both complexes are quantified using Hirshfeld surface analysis and their infrared spectra, electronic spectra and static magnetic properties are confronted with DFT and state-of-the-art ab-initio calculations. Dynamic magnetic measurements show that both complexes exhibit single-ion magnet behaviour induced by a magnetic field. Since they possess very similar chemical structure, differing only in the rigidity of the bridge between the magnetic centres, this chemical feature is put into context with changes in their magnetic relaxation. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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18 pages, 4345 KiB  
Article
Energy Levels in Pentacoordinate d5 to d9 Complexes
by Ján Titiš, Cyril Rajnák and Roman Boča
Inorganics 2022, 10(8), 116; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10080116 - 12 Aug 2022
Cited by 2 | Viewed by 1546
Abstract
Energy levels of pentacoordinate d5 to d9 complexes were evaluated according to the generalized crystal field theory at three levels of sophistication for two limiting cases of pentacoordination: trigonal bipyramid and tetragonal pyramid. The electronic crystal field terms involve the interelectron [...] Read more.
Energy levels of pentacoordinate d5 to d9 complexes were evaluated according to the generalized crystal field theory at three levels of sophistication for two limiting cases of pentacoordination: trigonal bipyramid and tetragonal pyramid. The electronic crystal field terms involve the interelectron repulsion and the crystal field potential; crystal field multiplets account for the spin–orbit interaction; and magnetic energy levels involve the orbital– and spin–Zeeman interactions with the magnetic field. The crystal field terms are labelled according to the irreducible representations of point groups D3h and C4v using Mulliken notation. The crystal field multiplets are labelled with the Bethe notations for the respective double groups D’3 and C’4. The magnetic functions, such as the temperature dependence of the effective magnetic moment and the field dependence of the magnetization, are evaluated by employing the apparatus of statistical thermodynamics as derivatives of the field-dependent partition function. When appropriate, the formalism of the spin Hamiltonian is applied, giving rise to a set of magnetic parameters, such as the zero-field splitting D and E, magnetogyric ratio tensor, and temperature-independent paramagnetism. The data calculated using GCFT were compared with the ab initio calculations at the CASSCF+NEVPT2 level and those involving the spin–orbit interaction. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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10 pages, 2628 KiB  
Perspective
Bis(benzimidazole) Complexes, Synthesis and Their Biological Properties: A Perspective
by Zdeněk Šindelář and Pavel Kopel
Inorganics 2023, 11(3), 113; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics11030113 - 09 Mar 2023
Cited by 7 | Viewed by 2104
Abstract
Benzimidazoles are a very well-known, broad group of compounds containing nitrogen atoms in their structure that can mimic properties of DNA bases. The compounds show not only biological activities but also are used for spectral and catalytic properties. Biological activity of benzimidazoles can [...] Read more.
Benzimidazoles are a very well-known, broad group of compounds containing nitrogen atoms in their structure that can mimic properties of DNA bases. The compounds show not only biological activities but also are used for spectral and catalytic properties. Biological activity of benzimidazoles can be tuned and accelerated in coordination compounds. This minireview is focused on preparation of bis(benzimidazoles), their complexes, and biological properties that can be found from 2015. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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19 pages, 1480 KiB  
Perspective
Integrative Metallomics Studies of Toxic Metal(loid) Substances at the Blood Plasma–Red Blood Cell–Organ/Tumor Nexus
by Maryam Doroudian and Jürgen Gailer
Inorganics 2022, 10(11), 200; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics10110200 - 07 Nov 2022
Cited by 8 | Viewed by 1574
Abstract
Globally, an estimated 9 million deaths per year are caused by human exposure to environmental pollutants, including toxic metal(loid) species. Since pollution is underestimated in calculations of the global burden of disease, the actual number of pollution-related deaths per year is likely to [...] Read more.
Globally, an estimated 9 million deaths per year are caused by human exposure to environmental pollutants, including toxic metal(loid) species. Since pollution is underestimated in calculations of the global burden of disease, the actual number of pollution-related deaths per year is likely to be substantially greater. Conversely, anticancer metallodrugs are deliberately administered to cancer patients, but their often dose-limiting severe adverse side-effects necessitate the urgent development of more effective metallodrugs that offer fewer off-target effects. What these seemingly unrelated events have in common is our limited understanding of what happens when each of these toxic metal(loid) substances enter the human bloodstream. However, the bioinorganic chemistry that unfolds at the plasma/red blood cell interface is directly implicated in mediating organ/tumor damage and, therefore, is of immediate toxicological and pharmacological relevance. This perspective will provide a brief synopsis of the bioinorganic chemistry of AsIII, Cd2+, Hg2+, CH3Hg+ and the anticancer metallodrug cisplatin in the bloodstream. Probing these processes at near-physiological conditions and integrating the results with biochemical events within organs and/or tumors has the potential to causally link chronic human exposure to toxic metal(loid) species with disease etiology and to translate more novel anticancer metal complexes to clinical studies, which will significantly improve human health in the 21st century. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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