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Synthesis, Characterization and Crystal Structure of Coordination Compounds

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

Deadline for manuscript submissions: closed (30 June 2022) | Viewed by 24383

Special Issue Editors

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
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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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.

Keywords

  • coordination compounds
  • complexes
  • crystal structure
  • polynuclear metal complexes
  • ligands
  • reactivity
  • applications

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Published Papers (12 papers)

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Research

Jump to: Review

15 pages, 5078 KiB  
Article
Sodium β-Diketonate Glyme Adducts as Precursors for Fluoride Phases: Synthesis, Characterization and Functional Validation
Molecules 2022, 27(19), 6282; https://doi.org/10.3390/molecules27196282 - 23 Sep 2022
Cited by 3 | Viewed by 1000
Abstract
Very few sodium complexes are available as precursors for the syntheses of sodium-based nanostructured materials. Herein, the diglyme, triglyme, and tetraglyme (CH3O(CH2CH2O)nCH3, n = 2–4) adducts of sodium hexafluoroacetylacetonate were synthesized in a [...] Read more.
Very few sodium complexes are available as precursors for the syntheses of sodium-based nanostructured materials. Herein, the diglyme, triglyme, and tetraglyme (CH3O(CH2CH2O)nCH3, n = 2–4) adducts of sodium hexafluoroacetylacetonate were synthesized in a single-step reaction and characterized by IR spectroscopy, 1H, and 13C NMR. Single-crystal X-ray diffraction studies provide evidence of the formation of the ionic oligomeric structure [Na4(hfa)6]2−•2[Na(diglyme2]+ when the diglyme is coordinated, while a mononuclear seven-coordinated complex Na(hfa)•tetraglyme is formed with the tetraglyme. Reaction with the monoglyme (CH3OCH2CH2OCH3) does not occur, and the unadducted polymeric structure [Na(hfa)]n forms, while the triglyme gives rise to a liquid adduct, Na(hfa)•triglyme•H2O. Thermal analysis data reveal great potentialities for their applications as precursors in metalorganic chemical vapor deposition (MOCVD) and sol-gel processes. As a proof-of-concept, the Na(hfa)•tetraglyme adduct was successfully applied to both the low-pressure MOCVD and the sol-gel/spin-coating synthesis of NaF films. Full article
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13 pages, 1999 KiB  
Article
High-Temperature Spin Crossover in Iron(II) Complexes with 2,6-Bis(1H-imidazol-2-yl)pyridine
Molecules 2022, 27(16), 5093; https://doi.org/10.3390/molecules27165093 - 10 Aug 2022
Cited by 4 | Viewed by 1356
Abstract
Novel iron(II) coordination compounds containing a ligand 2,6-bis(1H-imidazol-2-yl)pyridine (L), having such a composition as [FeL2]SO4·0.5H2O, [FeL2]Br2·H2O, [FeL2](ReO4)2, [FeL2]B10H10 [...] Read more.
Novel iron(II) coordination compounds containing a ligand 2,6-bis(1H-imidazol-2-yl)pyridine (L), having such a composition as [FeL2]SO4·0.5H2O, [FeL2]Br2·H2O, [FeL2](ReO4)2, [FeL2]B10H10∙H2O, [FeL2]B12H12∙1.5H2O had been synthesized and studied using UV-Vis (diffuse reflectance), infrared, extended X-ray absorption fine structure (EXAFS), and Mössbauer spectroscopy methods, as well as X-ray diffraction and static magnetic susceptibility methods. The analysis of the μeff(T) dependence in the temperature range of 80–600 K have shown that all the obtained complexes exhibit a high-temperature spin crossover 1A15T2. Full article
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17 pages, 1818 KiB  
Article
Theoretical Approach for the Luminescent Properties of Ir(III) Complexes to Produce Red–Green–Blue LEC Devices
Molecules 2022, 27(9), 2623; https://doi.org/10.3390/molecules27092623 - 19 Apr 2022
Cited by 1 | Viewed by 1690
Abstract
With an appropriate mixture of cyclometalating and ancillary ligands, based on simple structures (commercial or easily synthesized), it has been possible to design a family of eight new Ir(III) complexes (1A, 1B, 2B, 2C, 3B, 3C, 3D [...] Read more.
With an appropriate mixture of cyclometalating and ancillary ligands, based on simple structures (commercial or easily synthesized), it has been possible to design a family of eight new Ir(III) complexes (1A, 1B, 2B, 2C, 3B, 3C, 3D and 3E) useful as luminescent materials in LEC devices. These complexes involved the use of phenylpyridines or fluorophenylpyridines as cyclometalating ligands and bipyridine or phenanthroline-type structures as ancillary ligands. The emitting properties have been evaluated from a theoretical approach through Density Functional Theory and Time-Dependent Density Functional Theory calculations, determining geometric parameters, frontier orbital energies, absorption and emission energies, injection and transport parameters of holes and electrons, and parameters associated with the radiative and non-radiative decays. With these complexes it was possible to obtain a wide range of emission colours, from deep red to blue (701–440 nm). Considering all the calculated parameters between all the complexes, it was identified that 1B was the best red, 2B was the best green, and 3D was the best blue emitter. Thus, with the mixture of these complexes, a dual host–guest system with 3D-1B and an RGB (red–green–blue) system with 3D-2B-1B are proposed, to produce white LECs. Full article
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19 pages, 5294 KiB  
Article
The Theoretical and Experimental Investigation of the Fluorinated Palladium β-Diketonate Derivatives: Structure and Physicochemical Properties
Molecules 2022, 27(7), 2207; https://doi.org/10.3390/molecules27072207 - 28 Mar 2022
Viewed by 1645
Abstract
To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH3CXCHCO(R))2] with β-diketone [tfa−1,1,1-trifluoro-2,4-pentanedionato (1); pfpa−5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba−5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and β-iminoketone [i-tfa−1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa−5,5,6,6,6-pentafluoro-2-imino-4-hexanonato [...] Read more.
To search for new suitable Pd precursors for MOCVD/ALD processes, the extended series of fluorinated palladium complexes [Pd(CH3CXCHCO(R))2] with β-diketone [tfa−1,1,1-trifluoro-2,4-pentanedionato (1); pfpa−5,5,6,6,6-pentafluoro-2,4-hexanedionato (3); hfba−5,5,6,6,7,7,7-heptafluoro-2,4-heptanedionato (5)] and β-iminoketone [i-tfa−1,1,1-trifluoro-2-imino-4-pentanonato (2); i-pfpa−5,5,6,6,6-pentafluoro-2-imino-4-hexanonato (4); i-hfba-5,5,6,6,7,7,7-heptafluoro-2-imino-4-heptanonato (6)] ligands were synthesized with 70–80% yields and characterized by a set of experimental (SXRD, XRD, IR, NMR spectroscopy, TG) and theoretical (DFT, Hirshfeld surface analysis) methods. Solutions of Pd β-diketonates contained both cis and trans isomers, while only trans isomers were detected in the solutions of Pd β-iminoketonates. The molecules 26 and new polymorphs of complexes 3 and 5 were arranged preferentially in stacks, and the distance between molecules in the stack generally increased with elongation of the fluorine chain in ligands. The H…F contacts were the main ones involved in the formation of packages of molecules 12, and C…F, F…F, NH…F contacts appeared in the structures of complexes 46. The stability of complexes and their polymorphs in the crystal phases were estimated from DFT calculations. The TG data showed that the volatility differences between Pd β-iminoketonates and Pd β-diketonates were minimized with the elongation of the fluorine chain in the ligands. Full article
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6 pages, 538 KiB  
Communication
The Synthesis and Structure of a Scandium Nitrate Hydroxy-Bridged Dimeric Complex Supported by Bipyridyl Ligands
Molecules 2022, 27(6), 2024; https://doi.org/10.3390/molecules27062024 - 21 Mar 2022
Viewed by 1573
Abstract
The current discussion on whether scandium, yttrium and lanthanum should represent Group 3 in the Periodic Table or whether lutetium should replace lanthanum in the group has prompted us to further explore the structural chemistry of the Group 3 elements and compare the [...] Read more.
The current discussion on whether scandium, yttrium and lanthanum should represent Group 3 in the Periodic Table or whether lutetium should replace lanthanum in the group has prompted us to further explore the structural chemistry of the Group 3 elements and compare the coordination numbers and coordination geometries adopted. The steric and electronic properties of the coordinated ligands have a major influence on the structures adopted. We report the synthesis and crystal structure determination of an unusual dinuclear scandium complex [(bipy)(NO3)2Sc(µ-OH)2Sc(NO3)2(bipy)] obtained by the reaction of hydrated scandium nitrate with 2,2′-bipyridyl (bipy) in either ethanol or nitromethane. The crystal structure of the complex shows that the scandium centers are eight coordinate, and the structure obtained contrasts with related complexes found in the lanthanide series [Ln(bipy)2(NO3)3] and [Ln(phen)2(NO3)3] (phen = phenanthroline) and in [M(terpy)(NO3)3] (M = Sc, Er–Lu), where these complexes are all mononuclear. Full article
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21 pages, 14150 KiB  
Article
The Influence of Electrolyte Type on Kinetics of Redox Processes in the Polymer Films of Ni(II) Salen-Type Complexes
Molecules 2022, 27(6), 1812; https://doi.org/10.3390/molecules27061812 - 10 Mar 2022
Cited by 3 | Viewed by 1437
Abstract
Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and [...] Read more.
Electrodes modified with polymers derived from the complexes [Ni(salcn)], [Ni(salcn(Me))] and [Ni(salcn(Bu))] were obtained in order to study the kinetics of electrode processes occurring in polymer films, depending on the thickness of the films, the type of electrolyte and the solvent. FTIR and EQCM methods were used to determine the type of mass transported into polymer films during anode processes and the number of moles of ions and solvent. The rate of charge transport through films was determined by the cyclic voltammetry method, by the quantity cD1/2. It was shown that the charge transport was determined by the transport of anions. The kinetics were most efficient for poly[Ni(salcn(Bu))] modified electrodes, obtained from TBAPF6 and working in TBAClO4 and TBABF4. It was also shown that a solvent with a higher DN value and lower viscosity (MeCN) facilitated the transport of the charge through polymer films. Full article
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11 pages, 1362 KiB  
Article
Zn(II) and Co(II) 3D Coordination Polymers Based on 2-Iodoterephtalic Acid and 1,2-bis(4-pyridyl)ethane: Structures and Sorption Properties
Molecules 2022, 27(4), 1305; https://doi.org/10.3390/molecules27041305 - 15 Feb 2022
Cited by 4 | Viewed by 1843
Abstract
Metal-organic frameworks [M2(2-I-bdc)2bpe] (M = Zn(II) (1), Co(II) (2), 2-I-bdc = 2-iodoterephtalic acid, and bpe = 1,2-bis(4-pyridyl)ethane) were prepared and characterized by X-ray diffractometry. Both compounds retain their 3D structure after the removal of guest [...] Read more.
Metal-organic frameworks [M2(2-I-bdc)2bpe] (M = Zn(II) (1), Co(II) (2), 2-I-bdc = 2-iodoterephtalic acid, and bpe = 1,2-bis(4-pyridyl)ethane) were prepared and characterized by X-ray diffractometry. Both compounds retain their 3D structure after the removal of guest DMF molecules. Selectivity of sorption of different organic substrates from the gas phase was investigated for both complexes. Full article
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15 pages, 3323 KiB  
Article
Formation of Catalytically Active Nanoparticles under Thermolysis of Silver Chloroplatinate(II) and Chloroplatinate(IV)
Molecules 2022, 27(4), 1173; https://doi.org/10.3390/molecules27041173 - 09 Feb 2022
Cited by 3 | Viewed by 1403
Abstract
The thermal behaviour of Ag2[PtCl4] and Ag2[PtCl6] complex salts in inert and reducing atmospheres has been studied. The thermolysis of compounds in a helium atmosphere is shown to occur in two stages. At the first [...] Read more.
The thermal behaviour of Ag2[PtCl4] and Ag2[PtCl6] complex salts in inert and reducing atmospheres has been studied. The thermolysis of compounds in a helium atmosphere is shown to occur in two stages. At the first stage, the complexes decompose in the temperature range of 350–500 °C with the formation of platinum and silver chloride and the release of chlorine gas. At the second stage, silver chloride is sublimated in the temperature range of 700–900 °C, while metallic platinum remains in the solid phase. In contrast to the thermolysis of Ag2[PtCl6], the thermal decomposition of Ag2[PtCl4] at 350 °C is accompanied by significant heat release, which is associated with disproportionation of the initial salt to Ag2[PtCl6], silver chloride, and platinum metal. It is confirmed by DSC measurements, DFT calculations of a suggested reaction, and XRD. The thermolysis of Ag2[PtCl4] and Ag2[PtCl6] compounds is shown to occur in a hydrogen atmosphere in two poorly separable steps. The compounds are decomposed within 170–350 °C, and silver and platinum are reduced to a metallic state, while a metastable single-phase solid solution of Ag0.67Pt0.33 is formed. The catalytic activity of the resulting nanoalloy Ag0.67Pt0.33 is studied in the reaction of CO total (TOX) and preferential (PROX) oxidation. Ag0.67Pt0.33 enhanced Pt nano-powder activity in CO TOX, but was not selective in CO PROX. Full article
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15 pages, 5293 KiB  
Article
Structural Diversity of Silver Fluorinated β-Diketonates: Effect of the Terminal Substituent and Solvent
Molecules 2022, 27(3), 677; https://doi.org/10.3390/molecules27030677 - 20 Jan 2022
Cited by 4 | Viewed by 1557
Abstract
In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with β-diketonate ligands (R1C(O)CαHC(O)R2) we synthesized a series of the compounds containing tfac- (R1 [...] Read more.
In order to demonstrate the role of the fluorination and some solvents in the structural organization of the Ag(I) coordination polymers with β-diketonate ligands (R1C(O)CαHC(O)R2) we synthesized a series of the compounds containing tfac- (R1 = CH3, R2 = CF3) and pfpac- (R1 = CH3, R2 = C2F5) anions. Solvent-free [Ag(L)] (L = tfac 1, pfpac 2) compounds and the corresponding acetonitrile and toluene adducts have been characterized by elemental analysis and/or NMR, IR and single-crystal XRD. This series includes five new coordination polymers. Compound 1 is a 3D coordination framework based on Ag–Ochelate/bridge, Ag–Cα bonds, and argentophilic interactions. An increase in the fluorinated group leads to a chain coordination polymer 2 of an unusual structural organization. These chains can be represented as a “DNA-type”, where two intertwined helices based on Ag–Ochelate and Ag–Cα bonds are connected through Ag–Obridge ones. Two structural types of chain coordination polymers, [Ag(tfac)(CH3CN)] and [Ag2(L)2(solvent)], have been revealed for the adducts. The latter structural type differs significantly from the previously studied toluene and acetonitrile adducts of fluorinated Ag(I) β-diketonates of the same stoichiometry. Thermal analysis in helium showed that both 1 and 2 decompose to metallic silver with the compound of pfpac-ligand being slightly more stable. Full article
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20 pages, 2612 KiB  
Article
Thallium(I) Tropolonates: Synthesis, Structure, Spectral Characteristics, and Antimicrobial Activity Compared to Lead(II) and Bismuth(III) Analogues
Molecules 2022, 27(1), 183; https://doi.org/10.3390/molecules27010183 - 29 Dec 2021
Cited by 2 | Viewed by 1721
Abstract
Synthesis, single-crystal X-ray determination diffraction and FT-IR, NMR (1H, 13C, 19F and 205Tl), UV–vis, and luminescence spectra characteristics were described for series of thallium(I) compounds: thallium(I) triflate (Tl(OTf)), 1:1 co-crystals of thallium(I) triflate and tropolone (Htrop), Tl(OTf)·Htrop, as [...] Read more.
Synthesis, single-crystal X-ray determination diffraction and FT-IR, NMR (1H, 13C, 19F and 205Tl), UV–vis, and luminescence spectra characteristics were described for series of thallium(I) compounds: thallium(I) triflate (Tl(OTf)), 1:1 co-crystals of thallium(I) triflate and tropolone (Htrop), Tl(OTf)·Htrop, as well as simple thallium(I) chelates: Tl(trop) (1), Tl(5-metrop) (2), Tl(hino) (3), with Htrop, 5-methyltropolone (5-meHtrop), 4-isopropyltropolone (hinokitiol, Hhino), respectively, and additionally more complex {Tl@[Tl(hino)]6}(OTf) (4) compound. Comparison of their antimicrobial activity with selected lead(II) and bismuth(III) analogs and free ligands showed that only bismuth(III) complexes demonstrated significant antimicrobial activity, from two- to fivefold larger than the free ligands. Full article
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Review

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16 pages, 2986 KiB  
Review
Metalloporphyrin Metal–Organic Frameworks: Eminent Synthetic Strategies and Recent Practical Exploitations
Molecules 2022, 27(15), 4917; https://doi.org/10.3390/molecules27154917 - 02 Aug 2022
Cited by 5 | Viewed by 3998
Abstract
The emergence of metal–organic frameworks (MOFs) in recent years has stimulated the interest of scientists working in this area as one of the most applicable archetypes of three-dimensional structures that can be used as promising materials in several applications including but not limited [...] Read more.
The emergence of metal–organic frameworks (MOFs) in recent years has stimulated the interest of scientists working in this area as one of the most applicable archetypes of three-dimensional structures that can be used as promising materials in several applications including but not limited to (photo-)catalysis, sensing, separation, adsorption, biological and electrochemical efficiencies and so on. Not only do MOFs have their own specific versatile structures, tunable cavities, and remarkably high surface areas, but they also present many alternative procedures to overcome emerging obstacles. Since the discovery of such highly effective materials, they have been employed for multiple uses; additionally, the efforts towards the synthesis of MOFs with specific properties based on planned (template) synthesis have led to the construction of several promising types of MOFs possessing large biological or bioinspired ligands. Specifically, metalloporphyrin-based MOFs have been created where the porphyrin moieties are either incorporated as struts within the framework to form porphyrinic MOFs or encapsulated inside the cavities to construct porphyrin@MOFs which can combine the peerless properties of porphyrins and porous MOFs simultaneously. In this context, the main aim of this review was to highlight their structure, characteristics, and some of their prominent present-day applications. Full article
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15 pages, 2646 KiB  
Review
Metal Complexes or Chelators with ROS Regulation Capacity: Promising Candidates for Cancer Treatment
Molecules 2022, 27(1), 148; https://doi.org/10.3390/molecules27010148 - 27 Dec 2021
Cited by 16 | Viewed by 3473
Abstract
Reactive oxygen species (ROS) are rapidly eliminated and reproduced in organisms, and they always play important roles in various biological functions and abnormal pathological processes. Evaluated ROS have frequently been observed in various cancers to activate multiple pro-tumorigenic signaling pathways and induce the [...] Read more.
Reactive oxygen species (ROS) are rapidly eliminated and reproduced in organisms, and they always play important roles in various biological functions and abnormal pathological processes. Evaluated ROS have frequently been observed in various cancers to activate multiple pro-tumorigenic signaling pathways and induce the survival and proliferation of cancer cells. Hydrogen peroxide (H2O2) and superoxide anion (O2•−) are the most important redox signaling agents in cancer cells, the homeostasis of which is maintained by dozens of growth factors, cytokines, and antioxidant enzymes. Therefore, antioxidant enzymes tend to have higher activity levels to maintain the homeostasis of ROS in cancer cells. Effective intervention in the ROS homeostasis of cancer cells by chelating agents or metal complexes has already developed into an important anti-cancer strategy. We can inhibit the activity of antioxidant enzymes using chelators or metal complexes; on the other hand, we can also use metal complexes to directly regulate the level of ROS in cancer cells via mitochondria. In this review, metal complexes or chelators with ROS regulation capacity and with anti-cancer applications are collectively and comprehensively analyzed, which is beneficial for the development of the next generation of inorganic anti-cancer drugs based on ROS regulation. We expect that this review will provide a new perspective to develop novel inorganic reagents for killing cancer cells and, further, as candidates or clinical drugs. Full article
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