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Synthesis, Characterization and Crystal Structure of Coordination Compounds II
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Synthesis, Characterization and Crystal Structure of Coordination Compounds II

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

Deadline for manuscript submissions: closed (31 July 2023) | Viewed by 8839

Special Issue Editors

Dr. Sergey A. Adonin

E-Mail Website1 Website2
Guest Editor
Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Russia
Interests: p-block metals; bismuth; non-covalent interactions; halogen bonding; supramolecular chemistry
Special Issues, Collections and Topics in MDPI journals
Dr. Artem L. Gushchin

E-Mail Website
Guest Editor
Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Russia
Interests: coordination chemistry; transition metals; redox active ligands; noble metals; synthesis; reactivity; catalytic applications
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Coordination chemistry constitutes one of the most important and broad branches of modern chemistry. It is closely related to other areas including catalysis, biochemistry, photochemistry, materials science, etc.

This Special Issue welcomes all aspects of coordination chemistry, including the synthesis and characterization of new complexes; features of the supramolecular behavior of complexes; investigation of their structure both in solution and in solid state; design of novel materials based thereupon; insights into metal or free metal-catalyzed processes; the role of coordination compounds in biochemistry; photochemistry, etc.

Dr. Sergey A. Adonin
Dr. Artem L. Gushchin
Guest Editors

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. 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.

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Published Papers (6 papers)

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Research

22 pages, 7009 KiB  
Article
Crystal Structures of Xenon(VI) Salts: XeF5Ni(AsF6)3, XeF5AF6 (A = Nb, Ta, Ru, Rh, Ir, Pt, Au), and XeF5A2F11 (A = Nb, Ta)
by Zoran Mazej and Evgeny Goreshnik
Molecules 2023, 28(8), 3370; https://doi.org/10.3390/molecules28083370 - 11 Apr 2023
Viewed by 1124
Abstract
Experiments on the preparation of the new mixed cations XeF5M(AF6)3 (M = Cu, Ni; A = Cr, Nb, Ta, Ru, Rh, Re, Os, Ir, Pt, Au, As), XeF5M(SbF6)3 (M = Sn, Pb), and [...] Read more.
Experiments on the preparation of the new mixed cations XeF5M(AF6)3 (M = Cu, Ni; A = Cr, Nb, Ta, Ru, Rh, Re, Os, Ir, Pt, Au, As), XeF5M(SbF6)3 (M = Sn, Pb), and XeF5M(BF4)x(SbF6)3-x (x = 1, 2, 3; M = Co, Mn, Ni, Zn) salts were successful only in the preparation of XeF5Ni(AsF6)3. In other cases, mixtures of different products, mostly XeF5AF6 and XeF5A2F11 salts, were obtained. The crystal structures of XeF5Ni(AsF6)3, XeF5TaF6, XeF5RhF6, XeF5IrF6, XeF5Nb2F11, XeF5Ta2F11, and [Ni(XeF2)2](IrF6)2 were determined for the first time on single crystals at 150 K by X-ray diffraction. The crystal structures of XeF5NbF6, XeF5PtF6, XeF5RuF6, XeF5AuF6, and (Xe2F11)2(NiF6) were redetermined by the same method at 150 K. The crystal structure of XeF5RhF6 represents a new structural type in the family of XeF5AF6 salts, which crystallize in four different structural types. The XeF5A2F11 salts (M = Nb, Ta) are not isotypic and both represent a new structure type. They consist of [XeF5]+ cations and dimeric [A2F11]− anions. The crystal structure of [Ni(XeF2)2](IrF6)2 is a first example of a coordination compound in which XeF2 is coordinated to the Ni2+ cation. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Crystal Structure of Coordination Compounds II)
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14 pages, 3804 KiB  
Article
Two New 1D Supramolecular Compounds Based on PbI2 for Efficient Iodine Capture
by Xingxing Zhang, Jian Li and Yunyin Niu
Molecules 2023, 28(7), 2934; https://doi.org/10.3390/molecules28072934 - 24 Mar 2023
Cited by 2 | Viewed by 1129
Abstract
Two new inorganic-organic hybrid crystals based on PbI2 were assembled through the solvent evaporation method, namely, {[L1]·[Pb2I6]}n (1) and {[L2]2·[Pb3I10]}n (2). L1-L2 are a series of [...] Read more.
Two new inorganic-organic hybrid crystals based on PbI2 were assembled through the solvent evaporation method, namely, {[L1]·[Pb2I6]}n (1) and {[L2]2·[Pb3I10]}n (2). L1-L2 are a series of multivalent nitrogen-containing cationic ligands. Compounds 1–2 were characterized by single-crystal X-ray diffraction, elemental analysis, FT-IR, powder X-ray diffraction, and thermogravimetric microanalysis. The results showed that the adsorption rate of 80 mg compound 1 to iodine reached 96.59%, indicating a high iodine capture performance in cyclohexane solution. In the meantime, the adsorption kinetics is most suitable for a pseudo-second-order model, and the adsorption process is mainly chemisorption. Adsorption thermodynamics is most suitable for the Langmuir model, indicating that adsorption occurs on the surface of the monolayer. According to the adsorption mechanism, it can be inferred that the structure of compound 1 contains amino, benzene, N heterocyclic, and other active groups, that is, indirectly increases the adsorption site with iodine, and the chemical reaction with iodine improves the removal rate of iodine in cyclohexane solution. In addition, compound 1 was found to have good iodine adsorption and recyclability by cyclic experiments. Therefore, the synthesized compound 1 can be used as a potential and excellent iodide capture adsorbent, which may have a good application prospects in the future. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Crystal Structure of Coordination Compounds II)
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14 pages, 2475 KiB  
Article
Highly Luminescent Crystalline Sponge: Sensing Properties and Direct X-ray Visualization of the Substrates
by Pavel A. Demakov, Alexey A. Ryadun and Danil N. Dybtsev
Molecules 2022, 27(22), 8055; https://doi.org/10.3390/molecules27228055 - 19 Nov 2022
Cited by 5 | Viewed by 1623
Abstract
A phenomenon of crystalline sponge is represented by guest-dependent structural fluidity of the host polymeric lattice in highly crystalline sorbents, such as metal-organic frameworks, driven by multiple weak intermolecular interactions. Such induced fitting in MOFs is a valuable property in selective adsorption, guest [...] Read more.
A phenomenon of crystalline sponge is represented by guest-dependent structural fluidity of the host polymeric lattice in highly crystalline sorbents, such as metal-organic frameworks, driven by multiple weak intermolecular interactions. Such induced fitting in MOFs is a valuable property in selective adsorption, guest determination by single-crystal XRD and in-situ structural analysis under external stimuli. In this work, a porous three-dimensional metal-organic framework [Eu2(DMF)4(ttdc)3]·4.45DMF (1DMF; DMF = N,N-dimethylformamide, ttdc2– = trans-thienothiophenedicarboxylate anion) was applied as a crystalline sponge bearing luminescent functionality to couple its sensing properties with direct structural determination of the adsorbed molecules. As a result, the paper discusses crystal structures and luminescent properties for the successfully obtained new adducts with the crystallographic formulae [Eu2(DMSO)4(ttdc)3]·2.5DMSO·2.2H2O (1DMSO; DMSO = dimethylsulfoxide), [Eu2(DMF)4(ttdc)3]·3phet (1phet; phet = phenylethanal) and [Eu2(DMF)3.5(cin)0.5(ttdc)3]·1.64cin (1cin; cin = trans-cinnamaldehyde). As a result of inclusion of DMSO into 1, a slight increase in the quantum yield and excited state phosphorescence lifetime was observed, while the adsorption of phet leads to a considerable (up to three times) decrease in the corresponding values. The incorporation of cinnamal results in a full quenching of QY, from 20% down to zero, and a more than order of magnitude diminishing of the excited state lifetime compared to the initial 1DMF. The effective sensing of cinnamal was explained from the structural point of view by its direct coordination to the Eu3+ emitter, as well as by multiple weak intermolecular interactions with ttdc antenna ligand, both capable of enhancing the non-radiative energy dissipation. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Crystal Structure of Coordination Compounds II)
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13 pages, 2523 KiB  
Article
Variable Dimensionality of Europium(III) and Terbium(III) Coordination Compounds with a Flexible Hexacarboxylate Ligand
by Xiaolin Yu, Dmitry I. Pavlov, Alexey A. Ryadun, Andrei S. Potapov and Vladimir P. Fedin
Molecules 2022, 27(22), 7849; https://doi.org/10.3390/molecules27227849 - 14 Nov 2022
Cited by 4 | Viewed by 1542
Abstract
A reaction between 4,4′,4″-(benzene-1,3,5-triyltris(oxy))triphthalic acid (H6L) and lanthanide(III) nitrates (Ln = Eu3+, Tb3+) in water under the same conditions gave a molecular coordination compound [Tb(H4.5L)2(H2O)5]∙6H2O in the [...] Read more.
A reaction between 4,4′,4″-(benzene-1,3,5-triyltris(oxy))triphthalic acid (H6L) and lanthanide(III) nitrates (Ln = Eu3+, Tb3+) in water under the same conditions gave a molecular coordination compound [Tb(H4.5L)2(H2O)5]∙6H2O in the case of terbium(III) and a one-dimensional linear coordination polymer {[Eu2(H3L)2(H2O)6]∙8H2O}n in the case of europium(III). The crystal structures of both compounds were established by single-crystal X-ray diffraction, and they were further characterized by powder X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. The compounds demonstrated characteristic lanthanide-centered photoluminescence. The lanthanide-dependent dimensionality of the synthesized compounds, which are the first examples of the coordination compounds of hexacarboxylic acid H6L demonstrates its potential as a linker for new coordination polymers. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Crystal Structure of Coordination Compounds II)
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18 pages, 3831 KiB  
Article
Trapping of Ag+ into a Perfect Six-Coordinated Environment: Structural Analysis, Quantum Chemical Calculations and Electrochemistry
by Veronika I. Komlyagina, Nikolay F. Romashev, Vasily V. Kokovkin, Artem L. Gushchin, Enrico Benassi, Maxim N. Sokolov and Pavel A. Abramov
Molecules 2022, 27(20), 6961; https://doi.org/10.3390/molecules27206961 - 17 Oct 2022
Cited by 8 | Viewed by 1325
Abstract
Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[β-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by [...] Read more.
Self-assembly of (Bu4N)4[β-Mo8O26], AgNO3, and 2-bis[(2,6-diisopropylphenyl)-imino]acenaphthene (dpp-bian) in DMF solution resulted in the (Bu4N)2[β-{Ag(dpp-bian)}2Mo8O26] (1) complex. The complex was characterized by single crystal X-ray diffraction (SCXRD), X-ray powder diffraction (XRPD), diffuse reflectance (DR), infrared spectroscopy (IR), and elemental analysis. Comprehensive SCXRD studies of the crystal structure show the presence of Ag+ in an uncommon coordination environment without a clear preference for Ag-N over Ag-O bonding. Quantum chemical calculations were performed to qualify the nature of the Ag-N/Ag-O interactions and to assign the electronic transitions observed in the UV–Vis absorption spectra. The electrochemical behavior of the complex combines POM and redox ligand signatures. Complex 1 demonstrates catalytic activity in the electrochemical reduction of CO2. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Crystal Structure of Coordination Compounds II)
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21 pages, 6929 KiB  
Article
Binuclear Triphenylantimony(V) Catecholates through N-Donor Linkers: Structural Features and Redox Properties
by Andrey I. Poddel’sky, Ivan V. Smolyaninov, Aleksandra I. Shataeva, Evgenii V. Baranov and Georgy K. Fukin
Molecules 2022, 27(19), 6484; https://doi.org/10.3390/molecules27196484 - 01 Oct 2022
Cited by 1 | Viewed by 1252
Abstract
A series of binuclear triphenylantimony(V) bis-catecholato complexes 1–11 of the type (Cat)Ph3Sb-linker-SbPh3(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh3 with a neutral bidentate donor linker ligands pyrazine (Pyr), 4,4′-dipyridyl (Bipy), bis-(pyridine-4-yl)-disulfide (PySSPy), [...] Read more.
A series of binuclear triphenylantimony(V) bis-catecholato complexes 1–11 of the type (Cat)Ph3Sb-linker-SbPh3(Cat) was prepared by a reaction of the corresponding mononuclear catecholates (Cat)SbPh3 with a neutral bidentate donor linker ligands pyrazine (Pyr), 4,4′-dipyridyl (Bipy), bis-(pyridine-4-yl)-disulfide (PySSPy), and diazobicyclo[2,2,2]octane (DABCO) in a dry toluene: Cat = 3,6-di-tert-butyl-catecholate (3,6-DBCat), linker = Pyr (1); PySSPy (2); Bipy (3); DABCO (4); Cat = 3,5-di-tert-butyl-catecholate (3,5-DBCat), linker = Bipy (5); DABCO (9); Cat = 4,5-(piperazine-1,4-diyl)-3,6-di-tert-butylcatecholate (pip-3,6-DBCat), linker = Bipy (6); DABCO (10); Cat = 4,5-dichloro-3,6-di-tert-butylcatecholate (4,5-Cl2-3,6-DBCat), linker = Bipy (7); DABCO (11); and Cat = 4,5-dimethoxy-3,6-di-tert-butylcatecholate (4,5-(MeO)2-3,6-DBCat), linker = Bipy (8). The same reaction of (4,5-Cl2-3,6-DBCat)SbPh3 with DABCO in an open atmosphere results in a formation of 1D coordination polymer {[(4,5-Cl2-3,6-DBCat)SbPh3·H2O]·DABCO}n (12). Bis-catecholate complex Ph3Sb(Cat-Spiro-Cat)SbPh3 reacts with Bipy as 1:1 yielding a rare macrocyclic tetranuclear compound {Ph3Sb(Cat-Spiro-Cat)SbPh3∙(Bipy)}2 (13). The molecular structures of 1, 3, 4, 5, 8, 10, 12, and 13 in crystal state were established by single-crystal X-ray analysis. Complexes demonstrate different types of relative spatial positions of mononuclear moieties. The nature of chemical bonds, charges distribution, and the energy of Sb...N interaction were investigated in the example of complex 5. The electrochemical behavior of the complexes depends on the coordinated N-donor ligand. The coordination of pyrazine, Bipy, and PySSPy at the antimony atom changes their mechanism of electrooxidation: instead of two successive redox stages Cat/SQ and SQ/Cat, one multielectron stage was observed. The coordination of the DABCO ligand is accompanied by a significant shift in the oxidation potentials of the catecholate ligand to the cathodic region (by 0.4 V), compared to the initial complex. Full article
(This article belongs to the Special Issue Synthesis, Characterization and Crystal Structure of Coordination Compounds II)
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