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Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications

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A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Physical Chemistry and Chemical Physics".

Deadline for manuscript submissions: 20 April 2025 | Viewed by 9224

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Prof. Dr. Georgiy V. Girichev

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Department of Physics, Ivanovo State University of Chemistry and Technology, Sheremetevskiy Avenue 7, 153000 Ivanovo, Russia
Interests: molecular structure; intramolecular dynamics; thermodynamics; IR spectra; gas-phase electron diffraction; mass spectrometry; DFT and ab initio calculations
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Prof. Dr. Nina Giricheva

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Nanomaterial Research Institute, Ivanovo State University, 153025 Ivanovo, Russia
Interests: molecular structure; intramolecular dynamics, coordination compounds, gas-phase electron diffraction; IR spectroscopy, mass spectrometry, quantum chemical calculations

Special Issue Information

Dear Colleagues,

Coordination compounds of metals with organic ligands cover the widest class of chemical compounds and find various applications in the chemical industry, catalysis, microelectronics, sensors, medicine, pharmacology, etc. A powerful addition to the wide range of physical methods used to study this class of compounds are quantum chemical calculations, which constitute a dynamically progressing alternative to experiment.

Specialists in synthesis, molecular structure, vibrational and electronic spectroscopy, magnetic and catalytic chemistry, chemosensorics, and quantum chemical calculations are invited to submit their contributions to this Special Issue in accordance with its subject matter. Works that combine complementary experimental and theoretical studies are especially welcome.

Prof. Dr. Georgiy V. Girichev
Prof. Dr. Nina Giricheva
Guest Editors

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Published Papers (7 papers)

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Research

12 pages, 4403 KiB

Open AccessArticle

First Examples of s-Metal Complexes with Subporphyrazine and Its Phenylene-Annulated Derivatives: DFT Calculations

by Denis V. Chachkov, Oleg V. Mikhailov and Georgiy V. Girichev

Int. J. Mol. Sci. 2024, 25(13), 6897; https://doi.org/10.3390/ijms25136897 - 24 Jun 2024

Viewed by 719

Abstract

Using quantum chemical calculation data obtained by the DFT method with the B3PW91/TZVP and M062X/def2TZVP theory levels, the possibility of the existence of four Be(II) coordination compounds, each of which contains in the inner coordination sphere and the double deprotonated forms of subporphyrazine (H₂SP), mono[benzo]subporphyrazine (H₂MBSP), di[benzo]subporphyrazine (H₂DBSP), and tri[benzo]subporphyrazine (subphthalocyanine) (H₂TBSP) with a ratio Be(II) ion/ligand = 1:1, were examined Selected geometric parameters of the molecular structures of these (666)macrotricyclic complexes with closed contours are given; it was noted that BeN3 chelate nodes have a trigonal–pyramidal structure and exhibit a very significant (almost 30°) deviation from coplanarity; however, all three 6-membered metal-chelate and three 5-membered non-chelate rings in each of these compounds are practically planar and deviate from coplanarity by no more than 2.5°. The bond angles between two nitrogen atoms and a Be atom are equal to 60° (in the [BeSP] and [BeTBSP]) or less by no more than 0.5° (in the [BeMBSP] and [BeDBSP]). The presence of annulated benzo groups has little effect on the parameters of the molecular structures of these complexes. Good agreement between the structural data obtained using the above two versions of the DFT method was noticed. NBO analysis data for these complexes are presented; it was noted that, according to both DFT methods used, the ground state of the each of complexes under study is a spin singlet. Standard thermodynamic parameters of formation (standard enthalpy Δ_fH⁰, entropy S⁰, and Gibbs free energy Δ_fG⁰) for the above-mentioned macrocyclic compounds were calculated. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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17 pages, 10290 KiB

Open AccessArticle

Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes

by Julio Corredoira-Vázquez, Cristina González-Barreira, Jesús Sanmartín-Matalobos, Ana M. García-Deibe and Matilde Fondo

Int. J. Mol. Sci. 2024, 25(12), 6802; https://doi.org/10.3390/ijms25126802 - 20 Jun 2024

Viewed by 812

Abstract

Hexaazamacrocyclic Schiff bases have been extensively combined with lanthanoid (Ln) ions to obtain complexes with a highly axial geometry. However, the use of flexible hexaazatetraamine macrocycles containing two pyridines and acyclic spacers is rather uncommon. Accordingly, we obtained [DyL(OAc)₂]OAc·7H₂O·EtOH and [DyL^Me2(Cl)₂]Cl·2H₂O, where L and L^Me2 are the 18-membered macrocycles 3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane and 3,10-dimethyl-3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane, respectively, which contain ethylene and methylethylene spacers between their N₃ moieties. [DyL(OAc)₂]OAc·7H₂O·EtOH represents the first crystallographically characterized lanthanoid complex of L, while [DyL^Me2(Cl)₂]Cl·2H₂O contributes to increasing the scarce number of Ln^III compounds containing L^Me2. Furthermore, the crystal structure of L·12H₂O was solved, and it was compared with those of other related macrocycles previously published. Likewise, the crystal structures of the Dy^III complexes were compared with those of the lanthanoid and d-metal complexes of other 18-membered N₆ donor macrocycles. This comparison showed some effect of the spacers employed, as well as the influence of the size of the ancillary ligands and the metal ion. Additionally, the distinct folding behaviors of these macrocycles influenced their coordination geometries. Moreover, the luminescent properties of [DyL(OAc)₂]OAc·7H₂O·EtOH and [DyL^Me2(Cl)₂]Cl·2H₂O were also investigated, showing that both complexes are fluorescent, with the emission being sensitized by the ligands. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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13 pages, 4846 KiB

Open AccessArticle

XB₂Bi₂ (X = Si, Ge, Sn, Pb): Penta-Atomic Planar Tetracoordinate Si/Ge/Sn/Pb Clusters with 20 Valence Electrons

by Yan-Xia Jin and Jin-Chang Guo

Int. J. Mol. Sci. 2024, 25(5), 2819; https://doi.org/10.3390/ijms25052819 - 29 Feb 2024

Viewed by 954

Abstract

Planar tetracoordinate silicon, germanium, tin, and lead (ptSi/Ge/Sn/Pb) species are scarce and exotic. Here, we report a series of penta-atomic ptSi/Ge/Sn/Pb XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters with 20 valence electrons (VEs). Ternary XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters possess beautiful fan-shaped structures, with a Bi–B–B–Bi chain surrounding the central X core. The unbiased density functional theory (DFT) searches and high-level CCSD(T) calculations reveal that these ptSi/Ge/Sn/Pb species are the global minima on their potential energy surfaces. Born–Oppenheimer molecular dynamics (BOMD) simulations indicate that XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters are robust. Bonding analyses indicate that 20 VEs are perfect for the ptX XB₂Bi₂ (X = Si, Ge, Sn, Pb): two lone pairs of Bi atoms; one 5c–2e π, and three σ bonds (two Bi–X 2c–2e and one B–X–B 3c–2e bonds) between the ligands and X atom; three 2c–2e σ bonds and one delocalized 4c–2e π bond between the ligands. The ptSi/Ge/Sn/Pb XB₂Bi₂ (X = Si, Ge, Sn, Pb) clusters possess 2π/2σ double aromaticity, according to the (4n + 2) Hückel rule. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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17 pages, 2704 KiB

Open AccessArticle

Nickel(II) and Palladium(II) Complexes with η⁵:κ¹(N)-Coordinated Dicarbollide Ligands Containing Pendant Pyridine Group

by Dmitriy K. Semyonov, Marina Yu. Stogniy, Sergey A. Anufriev, Sergey V. Timofeev, Kyrill Yu. Suponitsky and Igor B. Sivaev

Int. J. Mol. Sci. 2023, 24(20), 15069; https://doi.org/10.3390/ijms242015069 - 11 Oct 2023

Viewed by 1259

Abstract

A series of C- and B-substituted nido-carborane derivatives with a pendant pyridyl group was prepared. The synthesized compounds were used as ligands in the complexation reactions with bis(triphenylphosphine)nickel(II) and palladium(II) chlorides to give six new metallacomplexes with unusual η⁵:κ¹(N)-coordination of the metal center. The single crystal structures of 1-(NC₅H₄-2′-S)-1,2-C₂B₁₀H₁₁, 1-(NC₅H₄-2′-CH₂S)-1,2-C₂B₁₀H₁₁, Cs [7-(NC₅H₄-2′-CH₂S)-7,8-C₂B₉H₁₁] closo- and nido-carboranes and 3-Ph₃P-3-(4(7)-NC₅H₄-2′-S)-closo-3,1,2-NiC₂B₉H₁₀ and 3-Ph₃P-3-(4(7)-NC₅H₄-2′-CH₂S)-closo-3,1,2-NiC₂B₉H₁₀ metallacarboranes were determined using single crystal X-ray diffraction. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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11 pages, 1313 KiB

Open AccessArticle

Effect of Linker Substituent Nature on Performance of Active Sites in UiO-66: Combined FT-IR and DFT Study

by Viktoriia V. Torbina, Mikhail A. Salaev, Evgeniy A. Paukshtis, Leonarda F. Liotta and Olga V. Vodyankina

Int. J. Mol. Sci. 2023, 24(19), 14893; https://doi.org/10.3390/ijms241914893 - 4 Oct 2023

Cited by 2 | Viewed by 1375

Abstract

The nature of organic linker substituents plays an important role in gas sorption and separation as well as in catalytic applications of metal–organic frameworks. Zirconium-based UiO-66 is one of the most tunable members of this class of materials. However, the prediction of its properties is still not a fully solved problem. Here, the infrared spectroscopic measurements using highly sensitive CO probe molecules, combined with DFT calculations, are used in order to characterize the performance of different acidic sites caused by the presence of different organic linker substituents. The proposed model allowed differentiation between various active sites over the UiO-66 and clarification of their behavior. The experimental IR bands related to CO adsorption can be unambiguously assigned to one type of site or another. The previously undescribed highly red-shifted band is attributed to CO adsorbed on coordinatively unsaturated zirconium sites through an O atom. The results confirm the lower and higher Lewis’s acidity of coordinatively unsaturated Zr sites on linker defects in the UiO-66 structure when electron-withdrawing and electron-donating groups are, respectively, included in a terephthalate moiety, whilst the Brønsted acidity of zirconium oxo-cluster remains almost unchanged. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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18 pages, 3001 KiB

Open AccessArticle

Ga···C Triel Bonds—Why They Are Not Strong Enough to Change Trigonal Configuration into Tetrahedral One: DFT Calculations on Dimers That Occur in Crystal Structures

by Sławomir J. Grabowski

Int. J. Mol. Sci. 2023, 24(15), 12212; https://doi.org/10.3390/ijms241512212 - 30 Jul 2023

Viewed by 1463

Abstract

Structures characterized by the trigonal coordination of the gallium center that interacts with electron rich carbon sites are described. These interactions may be classified as Ga···C triel bonds. Their properties are analyzed in this study since these interactions may be important in numerous chemical processes including catalytical activities; additionally, geometrical parameters of corresponding species are described. The Ga···C triel bonds discussed here, categorized also as the π-hole bonds, do not change the trigonal configuration of the gallium center into the tetrahedral one despite total interactions in dimers being strong; however, the main contribution to the stabilization of corresponding structures comes from the electrostatic forces. The systems analyzed theoretically here come from crystal structures since the Cambridge Structural Database, CSD, search was performed to find structures where the gallium center linked to CC bonds of Lewis base units occurs. The majority structures found in CSD are characterized by parallel, stacking-like arrangements of species containing the Ga-centers. The theoretical results show that interactions within dimers are not classified as the three-centers links as in a case of typical hydrogen bonds and numerous other interactions. The total interactions in dimers analyzed here consist of several local intermolecular atom–atom interactions; these are mainly the Ga···C links. The DFT results are supported in this study by calculations with the use of the quantum theory of atoms in molecules, QTAIM, the natural bond orbital, NBO, and the energy decomposition analysis, EDA, approaches. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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29 pages, 13570 KiB

Open AccessArticle

Nanomaterials Based on Collaboration with Multiple Partners: Zn₃Nb₂O₈ Doped with Eu³⁺ and/or Amino Substituted Porphyrin Incorporated in Silica Matrices for the Discoloration of Methyl Red

by Mihaela Birdeanu, Ion Fratilescu, Camelia Epuran, Liviu Mocanu, Catalin Ianasi, Anca Lascu and Eugenia Fagadar-Cosma

Int. J. Mol. Sci. 2023, 24(10), 8920; https://doi.org/10.3390/ijms24108920 - 17 May 2023

Viewed by 1532

Abstract

Designing appropriate materials destined for the removal of dyes from waste waters represents a great challenge for achieving a sustainable society. Three partnerships were set up to obtain novel adsorbents with tailored optoelectronic properties using silica matrices, Zn₃Nb₂O₈ oxide doped with Eu³⁺, and a symmetrical amino-substituted porphyrin. The pseudo-binary oxide with the formula Zn₃Nb₂O₈ was obtained by the solid-state method. The doping of Zn₃Nb₂O₈ with Eu³⁺ ions was intended in order to amplify the optical properties of the mixed oxide that are highly influenced by the coordination environment of Eu³⁺ ions, as confirmed by density functional theory (DFT) calculations. The first proposed silica material, based solely on tetraethyl orthosilicate (TEOS) with high specific surface areas of 518–726 m²/g, offered better performance as an adsorbent than the second one, which also contained 3-aminopropyltrimethoxysilane (APTMOS). The contribution of amino-substituted porphyrin incorporated into silica matrices resides both in providing anchoring groups for the methyl red dye and in increasing the optical properties of the whole nanomaterial. Two different types of methyl red adsorption mechanisms can be reported: one based on surface absorbance and one based on the dye entering the pores of the adsorbents due to their open groove shape network. Full article

(This article belongs to the Special Issue Metal-Organic Coordination Compounds: Synthesis, Structure, Spectra, Applications)

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