Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
6.7
4.6
Journals
Molecules
Special Issues
Recent Advances in Modern Inorganic Chemistry
molecules-logo
Submit to Molecules Review for Molecules Propose a Special Issue

Journal Menu

► Journal Menu

Journal Browser

► Journal Browser
share announcement

Recent Advances in Modern Inorganic Chemistry

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

Deadline for manuscript submissions: closed (30 April 2021) | Viewed by 46165

Special Issue Editor

Prof. Dr. Nikolay Gerasimchuk

E-Mail Website
Guest Editor
Department of Chemistry, Temple Hall 456, Missouri State University, Springfield, MO 65897, USA
Interests: synthesis, spectroscopic characterization, and medical-biological applications of oxime-based ligands and their Sb, Pd and Pt complexes; light-insensitive coordination polymers based on Ag(I)-cyanoximates and their colorimetric sensor/indicator applications; self-assembled nano-size 1D coordination polymers that emit in the NIR region; X-ray crystallography of small molecules

Special Issue Information

Dear Colleagues,

This Special Issue of Molecules is dedicated to recent advances in modern inorganic chemistry, which is a large discipline dealing with various aspects of this area of research. In the modern world of chemical studies, there is very little left from separate investigations in different branches of classic and inorganic chemistry. Instead, contemporary research clearly represents a multitude of interdisciplinary and largely collaborative efforts between other disciplines, such as physics (magnetism), physical chemistry (spectroscopy, catalysis), biology, biomedical sciences, medicinal chemistry, materials science, X-ray diffraction, etc. Moreover, today’s investigations are aimed not only at fundamental studies and basic research, but also at their societal usefulness and practicality. The present Special Issue is a compilation of novel, cutting-edge achievements in the most interesting areas of modern inorganic chemistry:

  • Synthesis and characterization of different types of Werner-type coordination compounds including coordination polymers;
  • Conventional wet-chemistry and solid-state preparation and investigations of new compounds—perspective materials;
  • Synthesis of organometallic compounds;
  • Bio-inorganic chemistry—investigations of structural and functional models of important natural metal-containing systems, and seeking new biologically active compounds to fight different diseases.  

This issue will contain the most recent results obtained in research laboratories of prominent inorganic chemists from around the world working in the described broad area of inorganic chemistry. As such, this Special Issue will be interesting to other chemists working in this field and beyond—all those who further advance science and human knowledge.

Prof. Dr. Nikolay Gerasimchuk
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 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. 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.

Keywords

  • coordination chemistry
  • organometallic chemistry
  • solid-state chemistry and new materials
  • bioinorganic chemistry

Published Papers (16 papers)

Download All Papers
Order results
Result details
Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:

Research

Jump to: Review

16 pages, 2723 KiB  
Article
Synthesis and Structure of the Bis- and Tris-Polyhedral Hybrid Carboranoclathrochelates with Functionalizing Biorelevant Substituents—The Derivatives of Propargylamine Iron(II) Clathrochelates with Terminal Triple C≡C Bond(s)
by Genrikh E. Zelinskii, Ilya P. Limarev, Anna V. Vologzhanina, Valentina A. Olshevskaya, Anton V. Makarenkov, Pavel V. Dorovatovskii, Alexander S. Chuprin, Mikhail A. Vershinin, Semyon V. Dudkin and Yan Z. Voloshin
Molecules 2021, 26(12), 3635; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26123635 - 14 Jun 2021
Cited by 1 | Viewed by 1689
Abstract
A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate [...] Read more.
A synthetic strategy for obtaining structurally flexible hybrid iron(II) carboranoclatrochelates functionalized with biorelevant groups, based on a combination of a 1,3-dipolar cycloaddition reaction with nucleophilic substitution of an appropriate chloroclathrochelate precursor, was developed. In its first stage, a stepwise substitution of the dichloroclathrochelate precursor with amine N-nucleophiles of different natures in various solvents was performed. One of its two chlorine atoms with morpholine or diethylamine in dichloromethane gave reactive monohalogenoclathrochelate complexes functionalized with abiorelevant substituents. Further nucleophilic substitution of their remaining chlorine atoms with propargylamine in DMF led to morpholine- and diethylamine-functionalized monopropargylamine cage complexes, the molecules of which contain the single terminal C≡C bond. Their “click” 1,3-cycloaddition reactions in toluene with ortho-carborane-(1)-methylazide catalyzed by copper(II) acetate gave spacer-containing di- and tritopic iron(II) carboranoclatrochelates formed by a covalent linking between their different polyhedral(cage) fragments. The obtained complexes were characterized using elemental analysis, MALDI-TOF mass, UV-Vis, 1H, 1H{11B}, 11B, 11B{1H}, 19F{1H} and 13C{1H}-NMR spectra, and by a single crystal synchrotron X-ray diffraction experiment for the diethylamine-functionalized iron(II) carboranoclathrochelate. Its encapsulated iron(II) ion is situated almost in the center of the FeN6-coordination polyhedron possessing a geometry intermediate between a trigonal prism and a trigonal antiprism with a distortion angle φ of approximately 28°. Conformation of this hybrid molecule is strongly affected by its intramolecular dihydrogen bonding: a flexibility of the carborane-terminated ribbed substituent allowed the formation of numerous C–H…H–B intramolecular interactions. The H(C) atom of this carborane core also forms the intermolecular C–H…F–B interaction with an adjacent carboranoclathrochelate molecule. The N–H…N intermolecular interaction between the diethylamine group of one hybrid molecule and the heterocyclic five-membered 1H-[1,2,3]-triazolyl fragment of the second molecule of this type caused formation of H-bonded carboranoclathrochelate dimers in the X-rayed crystal. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

23 pages, 4715 KiB  
Article
Third Generation Buchwald Precatalysts with XPhos and RuPhos: Multigram Scale Synthesis, Solvent-Dependent Isomerization of XPhos Pd G3 and Quality Control by 1H- and 31P-NMR Spectroscopy
by Svitlana O. Sotnik, Artem M. Mishchenko, Eduard B. Rusanov, Andriy V. Kozytskiy, Konstantin S. Gavrilenko, Sergey V. Ryabukhin, Dmitriy M. Volochnyuk and Sergey V. Kolotilov
Molecules 2021, 26(12), 3507; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26123507 - 09 Jun 2021
Cited by 2 | Viewed by 5190
Abstract
The third generation Buchwald precatalysts Pd(ABP)(Phos)(OMs) (also known as Phos Pd G3)) with XPhos and RuPhos were prepared in multigram scale by a modified procedure (ABP = fragment of C-deprotonated 2-aminobiphenyl, XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, RuPhos = 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl, OMs− = CH3SO [...] Read more.
The third generation Buchwald precatalysts Pd(ABP)(Phos)(OMs) (also known as Phos Pd G3)) with XPhos and RuPhos were prepared in multigram scale by a modified procedure (ABP = fragment of C-deprotonated 2-aminobiphenyl, XPhos = 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl, RuPhos = 2-dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl, OMs− = CH3SO3−). The 1H- and 31P-NMR spectra of the title complexes and some impurities, measured by various 1D and 2D techniques, were analyzed in detail. The solvent-dependent isomerization of Pd(ABP)(XPhos)(OMs) was studied by NMR, and the X-ray structures of two isomers were determined. The impurities in precatalysts, such as Pd(ABP)(HABP)(OMs) (HABP—neutral 2-aminobiphenyl coordinated to Pd2+ in N-monodentate mode) and PdCl2(XPhos)2, were identified and characterized by single crystal X-ray diffraction. A simple method for the quick quality control (QC) of the precatalysts, suitable for routine use, was proposed. The method was based on the assessment of the impurity content on the basis of the 1H-NMR spectra analysis. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

18 pages, 3245 KiB  
Article
Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies
by Christina D. Polyzou, Helen Nikolaou, Catherine P. Raptopoulou, Konstantis F. Konidaris, Vlasoula Bekiari, Vassilis Psycharis and Spyros P. Perlepes
Molecules 2021, 26(6), 1622; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26061622 - 15 Mar 2021
Cited by 3 | Viewed by 1650
Abstract
The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN [...] Read more.
The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln2(O2CMe)4(NO3)2(mepaoH)2] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the LnIII—mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O2CMe)3·4H2O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy2(O2CMe)6(mepaoH)2] (6). Treatment of 6 with one equivalent of HNO3 gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2–4 display similar structural characteristics with 1 and 5. The structures of 1–5 consist of dinuclear molecules in which the two LnIII centers are bridged by two bidentate bridging (η1:η1:μ2) and two chelating-bridging (η1:η2:μ2) acetate groups. The LnIII atoms are each chelated by a N,N’-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate LnIII centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the TbIII atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0–300 K range reveal weak antiferromagnetic intramolecular GdIII…GdIII exchange interactions in 3; the J value is −0.09(1) cm−1 based on the spin Hamiltonian Ĥ = −J(ŜGd1·ŜGd2). Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

30 pages, 5872 KiB  
Article
New Solids in As-O-Mo, As(P)-O-Mo(W) and As(P)-O-Nb(W) Systems That Exhibit Nonlinear Optical Properties
by Nikolay Gerasimchuk, Lauri Kivijarvi, Bruce Noll, Meriem Goudjil, Soma Khanra, Yu Ping, Miles Pearson and Frank Röminger
Molecules 2021, 26(5), 1494; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26051494 - 09 Mar 2021
Viewed by 2038
Abstract
Interactions between well-mixed fine powders of As2O3, P2O5, MoO3, WO3 and Nb2O5 at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum [...] Read more.
Interactions between well-mixed fine powders of As2O3, P2O5, MoO3, WO3 and Nb2O5 at different stoichiometry in quartz ampoules under vacuum at ~1000 °C in the presence of metallic molybdenum (or niobium), over several weeks, led to shiny dichroic crystalline materials being formed in cooler parts of the reaction vessel. An addition of small quantities of metals-Mo or Nb-was made with the aim of partially reducing their highly oxidized Mo(VI), W(VI) or Nb(V) species to corresponding Mo(V), W(V) and Nb(IV) centers, in order to form mixed valence solids. Sublimed crystals of four new compounds were investigated using a variety of techniques, with prime emphasis on the X-ray analysis, followed by spectroscopy (diffusion reflectance, IR, Raman and EPR), second harmonic generation (SHG), thermal analysis under N2 and air atmosphere, and single crystals electrical conductivity studies. The results evidenced the formation of new complex solids of previously unknown compositions and structures. Three out of four compounds crystallized in non-centrosymmetric space groups and represent layered 2D polymeric puckered structures that being stacked on each other form 3D lattices. All new solids exhibit strong second-harmonic-generation (SHG effect; based on YAG 1064 nm tests with detection of 532 nm photons), and a rare photosalient effect when crystals physically move in the laser beam. Single crystals’ electrical conductivity of the four new synthesized compounds was measured, and the results showed their semiconductor behavior. Values of band gaps of these new solids were determined using diffusion reflectance spectroscopy in the visible region. Aspects of new solids’ practical usefulness are discussed. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

21 pages, 40551 KiB  
Article
Slow Relaxation of the Magnetization in Anilato-Based Dy(III) 2D Lattices
by Samia Benmansour, Antonio Hernández-Paredes, María Bayona-Andrés and Carlos J. Gómez-García
Molecules 2021, 26(4), 1190; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26041190 - 23 Feb 2021
Cited by 9 | Viewed by 2250
Abstract
The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) [...] Read more.
The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) with two different anilato-type ligands (dianions of the 3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone: C6O4X22−, with X = H and Cl) in dimethyl sulfoxide (dmso). The two compounds prepared, formulated as: [Dy2(C6O4H2)3(dmso)2(H2O)2]·2dmso·18H2O (1) and [Dy2(C6O4Cl2)3(dmso)4]·2dmso·2H2O (2) show distorted hexagonal honeycomb layers with the solvent molecules (dmso and H2O) located in the interlayer space and in the hexagonal channels that run perpendicular to the layers. The magnetic measurements of compounds 1, 2 and [Dy2(C6O4(CN)Cl)3(dmso)6] (3), a recently reported related compound, show that the three compounds present slow relaxation of the magnetization. In compound 1 the SIM behaviour does not need the application of a DC field whereas 2 and 3 are field-induced SIM (FI-SIM) since they show slow relaxation of the magnetization when a DC field is applied. We discuss the differences observed in the crystal structures and magnetic properties based on the X group of the anilato ligands (H, Cl and Cl/CN) in 1–3 and in the recently reported derivative [Dy2(C6O4Br2)3(dmso)4]·2dmso·2H2O (4) with X = Br, that is also a FI-SIM. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

15 pages, 2942 KiB  
Article
Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes
by Anirban Karmakar, Anup Paul, Elia Pantanetti Sabatini, M. Fátima C. Guedes da Silva and Armando J. L. Pombeiro
Molecules 2021, 26(4), 1101; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26041101 - 19 Feb 2021
Cited by 10 | Viewed by 1961
Abstract
The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) [...] Read more.
The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Graphical abstract

29 pages, 9086 KiB  
Article
Versatile Reactivity of MnII Complexes in Reactions with N-Donor Heterocycles: Metamorphosis of Labile Homometallic Pivalates vs. Assembling of Endurable Heterometallic Acetates
by Ruslan A. Polunin, Igor S. Evstifeev, Olivier Cador, Stéphane Golhen, Konstantin S. Gavrilenko, Anton S. Lytvynenko, Nikolay N. Efimov, Vadim V. Minin, Artem S. Bogomyakov, Lahcène Ouahab, Sergey V. Kolotilov, Mikhail A. Kiskin and Igor L. Eremenko
Molecules 2021, 26(4), 1021; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26041021 - 15 Feb 2021
Cited by 4 | Viewed by 2390
Abstract
Reaction of 2,2′-bipyridine (2,2′-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)2(EtOH)]n led to the formation of binuclear complexes [Mn2(Piv)4L2] (L = 2,2′-bipy (1), phen (2); Piv− is the anion of pivalic [...] Read more.
Reaction of 2,2′-bipyridine (2,2′-bipy) or 1,10-phenantroline (phen) with [Mn(Piv)2(EtOH)]n led to the formation of binuclear complexes [Mn2(Piv)4L2] (L = 2,2′-bipy (1), phen (2); Piv− is the anion of pivalic acid). Oxidation of 1 or 2 by air oxygen resulted in the formation of tetranuclear MnII/III complexes [Mn4O2(Piv)6L2] (L = 2,2′-bipy (3), phen (4)). The hexanuclear complex [Mn6(OH)2(Piv)10(pym)4] (5) was formed in the reaction of [Mn(Piv)2(EtOH)]n with pyrimidine (pym), while oxidation of 5 produced the coordination polymer [Mn6O2(Piv)10(pym)2]n (6). Use of pyrazine (pz) instead of pyrimidine led to the 2D-coordination polymer [Mn4(OH)(Piv)7(µ2-pz)2]n (7). Interaction of [Mn(Piv)2(EtOH)]n with FeCl3 resulted in the formation of the hexanuclear complex [MnII4FeIII2O2(Piv)10(MeCN)2(HPiv)2] (8). The reactions of [MnFe2O(OAc)6(H2O)3] with 4,4′-bipyridine (4,4′-bipy) or trans-1,2-(4-pyridyl)ethylene (bpe) led to the formation of 1D-polymers [MnFe2O(OAc)6L2]n·2nDMF, where L = 4,4′-bipy (9·2DMF), bpe (10·2DMF) and [MnFe2O(OAc)6(bpe)(DMF)]n·3.5nDMF (11·3.5DMF). All complexes were characterized by single-crystal X-ray diffraction. Desolvation of 11·3.5DMF led to a collapse of the porous crystal lattice that was confirmed by PXRD and N2 sorption measurements, while alcohol adsorption led to porous structure restoration. Weak antiferromagnetic exchange was found in the case of binuclear MnII complexes (JMn-Mn = −1.03 cm−1 for 1 and 2). According to magnetic data analysis (JMn-Mn = −(2.69 ÷ 0.42) cm−1) and DFT calculations (JMn-Mn = −(6.9 ÷ 0.9) cm−1) weak antiferromagnetic coupling between MnII ions also occurred in the tetranuclear {Mn4(OH)(Piv)7} unit of the 2D polymer 7. In contrast, strong antiferromagnetic coupling was found in oxo-bridged trinuclear fragment {MnFe2O(OAc)6} in 11·3.5DMF (JFe-Fe = −57.8 cm−1, JFe-Mn = −20.12 cm−1). Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Graphical abstract

18 pages, 3806 KiB  
Article
Tuning π-Acceptor/σ-Donor Ratio of the 2-Isocyanoazulene Ligand: Non-Fluorinated Rival of Pentafluorophenyl Isocyanide and Trifluorovinyl Isocyanide Discovered
by Mason D. Hart, John J. Meyers, Jr., Zachary A. Wood, Toshinori Nakakita, Jason C. Applegate, Nathan R. Erickson, Nikolay N. Gerasimchuk and Mikhail V. Barybin
Molecules 2021, 26(4), 981; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26040981 - 12 Feb 2021
Cited by 3 | Viewed by 3138
Abstract
Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and [...] Read more.
Isocyanoazulenes (CNAz) constitute a relatively new class of isocyanoarenes that offers rich structural and electronic diversification of the organic isocyanide ligand platform. This article considers a series of 2-isocyano-1,3-X2-azulene ligands (X = H, Me, CO2Et, Br, and CN) and the corresponding zero-valent complexes thereof, [(OC)5Cr(2-isocyano-1,3-X2-azulene)]. Air- and thermally stable, X-ray structurally characterized 2-isocyano-1,3-dimethylazulene may be viewed as a non-benzenoid aromatic congener of 2,6-dimethyphenyl isocyanide (2,6-xylyl isocyanide), a longtime “workhorse” aryl isocyanide ligand in coordination chemistry. Single crystal X-ray crystallographic {Cr–CNAz bond distances}, cyclic voltametric {E1/2(Cr0/1+)}, 13C NMR {δ(13CN), δ(13CO)}, UV-vis {dπ(Cr) → pπ*(CNAz) Metal-to-Ligand Charge Transfer}, and FTIR {νN≡C, νC≡O, kC≡O} analyses of the [(OC)5Cr(2-isocyano-1,3-X2-azulene)] complexes provided a multifaceted, quantitative assessment of the π-acceptor/σ-donor characteristics of the above five 2-isocyanoazulenes. In particular, the following inverse linear relationships were documented: δ(13COtrans) vs. δ(13CN), δ(13COcis) vs. δ(13CN), and δ(13COtrans) vs. kC≡O,trans force constant. Remarkably, the net electron withdrawing capability of the 2-isocyano-1,3-dicyanoazulene ligand rivals those of perfluorinated isocyanides CNC6F5 and CNC2F3. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Graphical abstract

14 pages, 13713 KiB  
Article
A Molecular Tetrahedral Cobalt–Seleno-Based Complex as an Efficient Electrocatalyst for Water Splitting
by Ibrahim Munkaila Abdullahi, Jahangir Masud, Polydoros-Chrisovalantis Ioannou, Eleftherios Ferentinos, Panayotis Kyritsis and Manashi Nath
Molecules 2021, 26(4), 945; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26040945 - 10 Feb 2021
Cited by 13 | Viewed by 2995
Abstract
The cobalt–seleno-based coordination complex, [Co{(SePiPr2)2N}2], is reported with respect to its catalytic activity in oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solutions. An overpotential of 320 and 630 mV was [...] Read more.
The cobalt–seleno-based coordination complex, [Co{(SePiPr2)2N}2], is reported with respect to its catalytic activity in oxygen evolution and hydrogen evolution reactions (OER and HER, respectively) in alkaline solutions. An overpotential of 320 and 630 mV was required to achieve 10 mA cm−2 for OER and HER, respectively. The overpotential for OER of this CoSe4-containing complex is one of the lowest that has been observed until now for molecular cobalt(II) systems, under the reported conditions. In addition, this cobalt–seleno-based complex exhibits a high mass activity (14.15 A g−1) and a much higher turn-over frequency (TOF) value (0.032 s−1) at an overpotential of 300 mV. These observations confirm analogous ones already reported in the literature pertaining to the potential of molecular cobalt–seleno systems as efficient OER electrocatalysts. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

11 pages, 2907 KiB  
Article
Interplay between Oxo and Fluoro in Vanadium Oxyfluorides for Centrosymmetric and Non-Centrosymmetric Structure Formation
by Prashanth Sandineni, Hooman Yaghoobnejad Asl, Weiguo Zhang, P. Shiv Halasyamani, Kartik Ghosh and Amitava Choudhury
Molecules 2021, 26(3), 603; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26030603 - 24 Jan 2021
Cited by 1 | Viewed by 2318
Abstract
Herein, we report the syntheses of two lithium-vanadium oxide-fluoride compounds crystallized from the same reaction mixture through a time variation experiment. A low temperature hydrothermal route employing a viscous paste of V2O5, oxalic acid, LiF, and HF allowed the [...] Read more.
Herein, we report the syntheses of two lithium-vanadium oxide-fluoride compounds crystallized from the same reaction mixture through a time variation experiment. A low temperature hydrothermal route employing a viscous paste of V2O5, oxalic acid, LiF, and HF allowed the crystallization of one metastable phase initially, Li2VO0.55(H2O)0.45F5⋅2H2O (I), which on prolonged heating transforms to a chemically similar yet structurally different phase, Li3VOF5 (II). Compound I crystallizes in centrosymmetric space group, I2/a with a = 6.052(3), b = 7.928(4), c = 12.461(6) Å, and β = 103.99(2)°, while compound II crystallizes in a non-centrosymmetric (NCS) space group, Pna21 with a = 5.1173(2), b = 8.612(3), c = 9.346(3) Å. Synthesis of NCS crystals are highly sought after in solid-state chemistry for their second-harmonic-generation (SHG) response and compound II exhibits SHG activity albeit non-phase-matchable. In this article, we also describe their magnetic properties which helped in unambiguous assignment of mixed valency of V (+4/+5) for Li2VO0.55(H2O)0.45F5⋅2H2O (I) and +4 valency of V for Li3VOF5 (II). Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Graphical abstract

19 pages, 17099 KiB  
Article
Spectroelectrochemical Properties and Catalytic Activity in Cyclohexane Oxidation of the Hybrid Zr/Hf-Phthalocyaninate-Capped Nickel(II) and Iron(II) tris-Pyridineoximates and Their Precursors
by Yan Z. Voloshin, Semyon V. Dudkin, Svetlana A. Belova, Daniel Gherca, Dumitru Samohvalov, Corina-Mihaela Manta, Maria-Andreea Lungan, Samuel M. Meier-Menches, Peter Rapta, Denisa Darvasiová, Michal Malček, Armando J. L. Pombeiro, Luísa M. D. R. S. Martins and Vladimir B. Arion
Molecules 2021, 26(2), 336; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26020336 - 11 Jan 2021
Cited by 6 | Viewed by 3053
Abstract
The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV) and [...] Read more.
The in situ spectroelectrochemical cyclic voltammetric studies of the antimony-monocapped nickel(II) and iron(II) tris-pyridineoximates with a labile triethylantimony cross-linking group and Zr(IV)/Hf(IV) phthalocyaninate complexes were performed in order to understand the nature of the redox events in the molecules of heterodinuclear zirconium(IV) and hafnium(IV) phthalocyaninate-capped derivatives. Electronic structures of their 1e-oxidized and 1e-electron-reduced forms were experimentally studied by electron paramagnetic resonance (EPR) spectroscopy and UV−vis−near-IR spectroelectrochemical experiments and supported by density functional theory (DFT) calculations. The investigated hybrid molecular systems that combine a transition metal (pseudo)clathrochelate and a Zr/Hf-phthalocyaninate moiety exhibit quite rich redox activity both in the cathodic and in the anodic region. These binuclear compounds and their precursors were tested as potential catalysts in oxidation reactions of cyclohexane and the results are discussed. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

16 pages, 3362 KiB  
Article
Differential Precipitation of Mg(OH)2 from CaSO4·2H2O Using Citrate as Inhibitor—A Promising Concept for Reagent Recovery from MgSO4 Waste Streams
by Szilveszter Ziegenheim, Márton Szabados, Zoltán Kónya, Ákos Kukovecz, István Pálinkó and Pál Sipos
Molecules 2020, 25(21), 5012; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25215012 - 29 Oct 2020
Cited by 7 | Viewed by 2687
Abstract
In hydrometallurgical processing and acidic wastewater treatment, one of the neutralizing agents employed is MgO or Mg(OH)2. At the end of this process, the resulting solution, which is rich in SO42− and Mg2+ is treated with lime to [...] Read more.
In hydrometallurgical processing and acidic wastewater treatment, one of the neutralizing agents employed is MgO or Mg(OH)2. At the end of this process, the resulting solution, which is rich in SO42− and Mg2+ is treated with lime to remove (or minimize the amount) of these ions via the precipitation of Mg(OH)2 and CaSO4·2H2O (gypsum). In our work, an attempt was made to separate the two solids by increasing the induction time of the gypsum precipitation, thus regenerating relatively pure Mg(OH)2 which could be reused in wastewater treatments or hydrometallurgical processing circuits, and in this way, significantly enhancing the economic viability of the process. During our experiments, the reaction of an MgSO4 solution with milk of lime prepared from quicklime was studied. The effects of a range of organic additives, which can slow down the precipitation of gypsum have been assessed. The process was optimized for the most promising inhibiting agent—that is, the citrate ion. The reactions were continuously monitored in situ by conductometric measurements with parallel monitoring of solution pH and temperature. ICP-OES measurements were also carried out on samples taken from the reaction slurry. The composition of the precipitating solids at different reaction times was established by powder XRD and their morphology by SEM. Finally, experiments were carried out to locate the additive after the completion of the precipitation reaction to get information about its potential reuse. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

14 pages, 4345 KiB  
Article
The Structure and Thermal Properties of Solid Ternary Compounds Forming with Ca2+, Al3+ and Heptagluconate Ions
by Ákos Buckó, Zsolt Kása, Márton Szabados, Bence Kutus, Ottó Berkesi, Zoltán Kónya, Ákos Kukovecz, Pál Sipos and István Pálinkó
Molecules 2020, 25(20), 4715; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25204715 - 14 Oct 2020
Viewed by 2063
Abstract
In the present work, the structure and thermal stability of Ca–Al mixed-metal compounds, relevant in the Bayer process as intermediates, have been investigated. X-ray diffraction (XRD) measurements revealed the amorphous morphology of the compounds, which was corroborated by SEM-EDX measurements. The results of [...] Read more.
In the present work, the structure and thermal stability of Ca–Al mixed-metal compounds, relevant in the Bayer process as intermediates, have been investigated. X-ray diffraction (XRD) measurements revealed the amorphous morphology of the compounds, which was corroborated by SEM-EDX measurements. The results of ICP-OES and UV-Vis experiments suggested the formation of three possible ternary calcium aluminum heptagluconate (Ca-Al-Hpgl) compounds, with the formulae of CaAlHpgl(OH)40, Ca2AlHpgl2(OH)50 and Ca3Al2Hpgl3(OH)90. Additional IR and Raman experiments revealed the centrally symmetric arrangement of heptagluconate around the metal ion. The increased thermal stability was demonstrated by thermal analysis of the solids and confirmed our findings. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

16 pages, 2821 KiB  
Article
Water-Soluble Bismuth(III) Polynuclear Tyrosinehydroximate Metallamacrocyclic Complex: Structural Parallels to Lanthanide Metallacrowns
by Marina A. Katkova, Grigory Y. Zhigulin, Roman V. Rumyantcev, Galina S. Zabrodina, Vladimir R. Shayapov, Maxim N. Sokolov and Sergey Y. Ketkov
Molecules 2020, 25(19), 4379; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25194379 - 23 Sep 2020
Cited by 11 | Viewed by 2768
Abstract
Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth—elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived [...] Read more.
Recently there has been a great deal of interest and associated research into aspects of the coordination chemistry of lanthanides and bismuth—elements that show intriguing common features. This work focuses on the synthesis and characterization of a novel bismuth(III) polynuclear metallamacrocyclic complex derived from aminohydroxamic acid, in order to compare the coordination ability of Bi3+ with the similarly sized La3+ ions. A polynuclear tyrosinehydroximate Bi(OH)[15-MCCu(II)Tyrha-5](NO3)2 (1) was obtained according to the synthetic routes previously described for water-soluble Ln(III)-Cu(II) 15-MC-5 metallacrowns. Correlations between structural parameters of Bi(III) and Ln(III) complexes were analyzed. DFT calculations confirmed the similarity between molecular structures of the model bismuth(III) and lanthanum(III) tyrosinehydroximate 15-metallacrowns-5. Analysis of the electronic structures revealed, however, stronger donor-acceptor interactions between the central ion and the metallamacrocycle in the case of the lanthanum analogue. Thermochromic properties of 1 were studied. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Graphical abstract

15 pages, 2113 KiB  
Article
N-Alkylaminoferrocene-Based Prodrugs Targeting Mitochondria of Cancer Cells
by Viktor Reshetnikov, Hülya Gizem Özkan, Steffen Daum, Christina Janko, Christoph Alexiou, Caroline Sauer, Markus R. Heinrich and Andriy Mokhir
Molecules 2020, 25(11), 2545; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules25112545 - 29 May 2020
Cited by 16 | Viewed by 3802
Abstract
Intracellular concentration of reactive oxygen species (e.g., H2O2) in cancer cells is elevated over 10-fold as compared to normal cells. This feature has been used by us and several other research groups to design cancer specific prodrugs, for example, [...] Read more.
Intracellular concentration of reactive oxygen species (e.g., H2O2) in cancer cells is elevated over 10-fold as compared to normal cells. This feature has been used by us and several other research groups to design cancer specific prodrugs, for example, N-alkylaminoferrocene (NAAF)-based prodrugs. Further improvement of the efficacy of these prodrugs can be achieved by their targeting to intracellular organelles containing elevated reactive oxygen species (ROS) amounts. For example, we have previously demonstrated that lysosome-targeted NAAF-prodrugs exhibit higher anticancer activity in cell cultures, in primary cells and in vivo (Angew. Chem. Int. Ed. 2017, 56, 15545). Mitochondrion is an organelle, where electrons can leak from the respiratory chain. These electrons can combine with O2, generating O2−• that is followed by dismutation with the formation of H2O2. Thus, ROS can be generated in excess in mitochondria and targeting of ROS-sensitive prodrugs to these organelles could be a sensible possibility for enhancing their efficacy. We have previously reported on NAAF-prodrugs, which after their activation in cells, are accumulated in mitochondria (Angew. Chem. Int. Ed. 2018, 57, 11943). Now we prepared two hybrid NAAF-prodrugs directly accumulated in mitochondria and activated in these organelles. We studied their anticancer activity and mode of action. Based on these data, we concluded that ROS produced by mitochondria is not available in sufficient quantities for activation of the ROS-responsive prodrugs. The reason for this can be efficient scavenging of ROS by antioxidants. Our data are important for the understanding of the mechanism of action of ROS-activatable prodrugs and will facilitate their further development. Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

Review

Jump to: Research

15 pages, 5025 KiB  
Review
57Fe Mössbauer Spectroscopy as a Tool for Study of Spin States and Magnetic Interactions in Inorganic Chemistry
by Ernő Kuzmann, Zoltán Homonnay, Zoltán Klencsár and Roland Szalay
Molecules 2021, 26(4), 1062; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26041062 - 18 Feb 2021
Cited by 11 | Viewed by 3890
Abstract
In this mini-review of our research group’s activity, the application of 57Fe Mössbauer spectroscopy in studies of electronic structure, coordination environment, and magnetic interactions in an interesting series of Fe(II/III) compounds selected is discussed. We selected two prominent phenomena that arose during [...] Read more.
In this mini-review of our research group’s activity, the application of 57Fe Mössbauer spectroscopy in studies of electronic structure, coordination environment, and magnetic interactions in an interesting series of Fe(II/III) compounds selected is discussed. We selected two prominent phenomena that arose during investigations of selected groups of compounds carried out at different periods of time: (1) very high magnetic hyperfine fields observed at low temperatures; (2) changes in the oxidation state of the central iron atom of complexes in the solid state during interactions with gaseous O2/H2O mixtures, resulting in spin crossover (SCO). Full article
(This article belongs to the Special Issue Recent Advances in Modern Inorganic Chemistry)
►▼ Show Figures

Figure 1

Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:
 
Displaying articles 1-16
Back to TopTop