Editor’s Choice Articles

Editor’s Choice articles are based on recommendations by the scientific editors of MDPI journals from around the world. Editors select a small number of articles recently published in the journal that they believe will be particularly interesting to readers, or important in the respective research area. The aim is to provide a snapshot of some of the most exciting work published in the various research areas of the journal.

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13 pages, 1153 KiB  
Article
Redox Targets for Phosphine–Boranes
by Yonatan Morocz, Rachel E. Greben and Leonard A. Levin
Inorganics 2023, 11(7), 310; https://doi.org/10.3390/inorganics11070310 - 22 Jul 2023
Cited by 1 | Viewed by 1022
Abstract
Understanding the complex mechanisms underlying redox-mediated biological processes is a fundamental pillar of cellular biology. We describe the identification and quantification of disulfide formation and reduction in response to phosphine–borane complexes. We illustrate the specific cysteine reduction effects of the novel phosphine–borane complex [...] Read more.
Understanding the complex mechanisms underlying redox-mediated biological processes is a fundamental pillar of cellular biology. We describe the identification and quantification of disulfide formation and reduction in response to phosphine–borane complexes. We illustrate the specific cysteine reduction effects of the novel phosphine–borane complex bis(3-propionic acid methyl ester) phenylphosphine–borane complex (PB1) on cultured 661W cells. A total of 1073 unique protein fragments from 628 unique proteins were identified and quantified, of which 13 were found to be statistically significant in comparison to control cells. Among the 13 identified proteins were Notch1, HDAC1, UBA1, USP7, and subunits L4 and L7 of the 60S ribosomal subunit, all of which are involved in redox or cell death-associated pathways. Leveraging the ability of tandem mass tagging mass spectrometry to provide quantitative data in an exploratory manner provides insight into the effect PB1 and other phosphine–borane compounds may have on the cysteine redoxome. Full article
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12 pages, 3812 KiB  
Article
Improved Oxide Ion Conductivity of Hexagonal Perovskite-Related Oxides Ba3W1+xV1−xO8.5+x/2
by Yugo Kikuchi, Yuta Yasui, James R. Hester and Masatomo Yashima
Inorganics 2023, 11(6), 238; https://doi.org/10.3390/inorganics11060238 - 29 May 2023
Cited by 3 | Viewed by 1199
Abstract
Hexagonal perovskite-related oxides such as Ba3WVO8.5 have attracted much attention due to their unique crystal structures and significant oxide ion conduction. However, the oxide ion conductivity of Ba3WVO8.5 is not very high. Herein, we report new hexagonal [...] Read more.
Hexagonal perovskite-related oxides such as Ba3WVO8.5 have attracted much attention due to their unique crystal structures and significant oxide ion conduction. However, the oxide ion conductivity of Ba3WVO8.5 is not very high. Herein, we report new hexagonal perovskite-related oxides Ba3W1+xV1−xO8.5+x/2 (x = −0.1, −0.05, 0.05, 0.1, 0.25, 0.4, 0.5, 0.6, and 0.75). The bulk conductivity of Ba3W1.6V0.4O8.8 was found to be 21 times higher than that of the mother material Ba3WVO8.5 at 500 °C. Maximum entropy method (MEM) neutron scattering length density (NSLD) analyses of neutron diffraction data at 800 °C experimentally visualized the oxide ion diffusion pathways through the octahedral O2 and tetrahedral O3 sites in intrinsically oxygen-deficient layers. By increasing the excess W content x in Ba3W1+xV1−xO8.5+x/2, the excess oxygen content x/2 increases, which leads to more oxygen atoms at the O2 and O3 oxygen sites, a higher minimum NSLD on the O2–O3 path, and a higher level of conductivity. Another reason for the increased conductivity of Ba3W1.6V0.4O8.8 is the lower activation energy for oxide ion conduction, which can be ascribed to the longer (W/V)–O2 and (W/V)–O3 distances due to the substitution of V atoms with large-sized W species. The present findings open new avenues in the science and technology of oxide ion conductors. Full article
(This article belongs to the Special Issue Layered Perovskites: Synthesis, Properties and Structures)
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17 pages, 5497 KiB  
Article
Chalcogen Bonds, Halogen Bonds and Halogen···Halogen Contacts in Di- and Tri-iododiorganyltellurium(IV) Derivatives
by Sergi Burguera, Rosa M. Gomila, Antonio Bauzá and Antonio Frontera
Inorganics 2023, 11(5), 209; https://doi.org/10.3390/inorganics11050209 - 12 May 2023
Cited by 1 | Viewed by 1212
Abstract
In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in [...] Read more.
In this manuscript, we have examined the CSD (Cambridge Structural Database) to investigate the relative ability of Te and I (in practice, the heaviest chalcogen and halogen atoms) in di- and tri-iododiorganyltellurium(IV) derivatives to establish σ-hole interactions. The geometry around the Te(IV) in this type of compound is trigonal bipyramidal where the stereoactive lone pair at Te(IV) occupies one of the equatorial positions. In the solid state, Te(IV) tends to form pseudo-octahedral coordination by establishing strong noncovalent interactions opposite to the two covalent bonds of the equatorial plane. Such contacts can also be classified as chalcogen bonds following the recommendation of the International Union of Pure and Applied Chemistry (IUPAC). Such contacts have been analyzed energetically in this work using density functional theory (DFT) calculations, rationalized using molecular electrostatic potential (MEP) surface analysis and characterized using a combination of the quantum theory of atoms in molecules (QTAIM) and noncovalent interaction plot (NCIplot) computational tools. Finally, the observation of halogen bonds and type I halogen···halogen contacts is also emphasized and compared to the chalcogen bonds. Energy decomposition analysis has also been performed to compare the physical nature of chalcogen, halogen and type I interactions. Full article
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14 pages, 2933 KiB  
Article
X-ray Absorption Spectroscopy of Phosphine-Capped Au Clusters
by Shailendra K. Sharma, Bernt Johannessen, Vladimir B. Golovko and Aaron T. Marshall
Inorganics 2023, 11(5), 191; https://doi.org/10.3390/inorganics11050191 - 28 Apr 2023
Cited by 1 | Viewed by 1550
Abstract
The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric [...] Read more.
The structural determination of ultrasmall clusters remains a challenge due to difficulties in crystallisation. Often the atomically precise clusters undergo structural change under the influence of the environment. X-ray absorption spectroscopy (XAS) can be an attractive tool to study the electronic and geometric properties of such clusters deposited onto various supports under in situ conditions. Herein, [Au6(dppp)4](NO3)2, [Au9(PPh3)8](NO3)3, [Au13(dppe)5Cl2]Cl3, and Au101(PPPh3)21Cl5 clusters were studied using XAS. The clusters exhibited distinct features compared to bulk gold. XANES results show a systematic increase in the absorption edge energy and white line intensity, with a decrease in cluster nuclearity. The EXAFS of clusters are sensitive to nuclearity and ligands and were fitted with their known crystal structures. This study advances the understanding of the phosphine-ligated metal clusters relevant to practical applications in catalysis and sensing. Full article
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19 pages, 2502 KiB  
Article
C–H Metalation of Terpyridine Stereoisomers with Ni(II), Pd(II), and Pt(II)
by Leo Payen, Lukas Kletsch, Tobias Lapić, Mathias Wickleder and Axel Klein
Inorganics 2023, 11(4), 174; https://doi.org/10.3390/inorganics11040174 - 21 Apr 2023
Cited by 2 | Viewed by 1592
Abstract
Ni(II), Pd(II), and Pt(II) complexes [M(Y-terpy)X] (X = Cl or Br) containing the tridentate N^C^N-cyclometalating 2,3′:5′,2″and 2,2′:4′,2″ stereoisomers of the well-known tridentate N^N^N ligand 2,2′:6′,2″-terpyridine (terpy) were synthesised in moderate to good yields through C–H activation. For the Pt complexes, the phenyl ethynide [...] Read more.
Ni(II), Pd(II), and Pt(II) complexes [M(Y-terpy)X] (X = Cl or Br) containing the tridentate N^C^N-cyclometalating 2,3′:5′,2″and 2,2′:4′,2″ stereoisomers of the well-known tridentate N^N^N ligand 2,2′:6′,2″-terpyridine (terpy) were synthesised in moderate to good yields through C–H activation. For the Pt complexes, the phenyl ethynide derivatives [Pt(Y-terpy)(C≡CPh)] were also obtained under Sonogashira conditions. In contrast to this, C^N^N cyclometalated complexes using the 2,2′:6′,3″- and 2,2′:6′4″-terpy isomers were not obtained. Comparison of the N^C^N complexes of the cyclometalated 2,3′:5′,2″- and 2,2′:4′,2″-terpy ligands with complexes [M(dpb)Cl] of the prototypical N^C^N cyclometalating ligand dpb (Hdpb = 2,6-diphenyl-pyridine) showed higher potentials for the terpy complexes for the ligand-centred reductions in line with the superior π-accepting properties of the terpy ligands compared with dpb. Metal-centred oxidations were facilitated by the dpb ligand carrying a central σ-donating phenyl group instead of a metalated pyridine moiety. The same trends were found for the long-wavelength absorptions and the derived electrochemical and optical band gaps. The lower σ-donating capacities of the cyclometalated terpy derivatives is also confirmed by a reduced trans influence in the structure of [Ni(2,3′:5′,2″-terpy)Br0.14/OAc0.86]. Attempts to re-crystallise some poorly soluble Pd(II) and Pt(II) complexes of this series under solvothermal conditions (HOAc) gave two structures with N-protonated cyclometalated pyridine moieties, [Pt(2,3′:5′,2″-terpyH)Cl].Cl and [Pd(2,3′:5′,2″-terpyH)Cl2]. Full article
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12 pages, 1967 KiB  
Article
Surface Passivation of Organic-Inorganic Hybrid Perovskites with Methylhydrazine Iodide for Enhanced Photovoltaic Device Performance
by Chongzhu Hu, Zhuangzhuang Zhang, Jun Chen and Peng Gao
Inorganics 2023, 11(4), 168; https://doi.org/10.3390/inorganics11040168 - 16 Apr 2023
Cited by 6 | Viewed by 1680
Abstract
Organic-inorganic hybrid perovskites are highly efficient in photovoltaic applications, making the commercialization of perovskite solar cells (PSCs) possible. However, the high density of defects on the surface significantly affects the performance of PSCs. To address this issue, we have demonstrated a facile post-treatment [...] Read more.
Organic-inorganic hybrid perovskites are highly efficient in photovoltaic applications, making the commercialization of perovskite solar cells (PSCs) possible. However, the high density of defects on the surface significantly affects the performance of PSCs. To address this issue, we have demonstrated a facile post-treatment strategy utilizing methylhydrazine iodide (MHyI) to passivate the surface of the perovskite film. MHyI could co-ordinate with the dangling bonds on the surface of perovskite films, effectively passivating defects in the film and suppressing carrier non-radiative recombination. As a result, PSCs with MHyI modification exhibit a champion power conversion efficiency (PCE) of 23.19% and a high open-circuit voltage (VOC) of 1.14 V (0.43 V voltage deficit). Moreover, unencapsulated solar cells maintain their initial efficiency of 88% after 30 days of exposure to ambient air with 30% humidity, and the devices with encapsulation retained 57% of their initial efficiency after 200 h of maximum power point (MPP) loading under constant light irradiation in ambient air. Overall, our results provide a facile method for improving the performance and stability of PSCs. Full article
(This article belongs to the Section Inorganic Materials)
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12 pages, 1089 KiB  
Article
Dibromo–Isonitrile and N-acyclic Carbene Complexes of Platinum(II): Synthesis and Reactivity
by Anna Farasat, Francesca Nerli, Luca Labella, Marco Taddei and Simona Samaritani
Inorganics 2023, 11(4), 137; https://doi.org/10.3390/inorganics11040137 - 23 Mar 2023
Cited by 1 | Viewed by 1217
Abstract
A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from trans-[Pt(μ-Br)Br(PPh3)]2 and according to a protocol previously optimized for the preparation of analogous chlorinated compounds. In the first step of the synthesis, the ring opening of [...] Read more.
A series of dibromo-N-acyclic (NAC) carbene complexes of platinum(II) were synthesized, starting from trans-[Pt(μ-Br)Br(PPh3)]2 and according to a protocol previously optimized for the preparation of analogous chlorinated compounds. In the first step of the synthesis, the ring opening of the dinuclear precursor was carried out using suitable isonitrile ligands, while the following step consisted of the addition of N,N-diethylamine to the products obtained in the first step. The two reactions were separately investigated, and attention was given to the differences between brominated and chlorinated systems. Full article
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30 pages, 10177 KiB  
Article
The Electronic Nature of Cationic Group 10 Ylidyne Complexes
by Leonard R. Maurer, Jens Rump and Alexander C. Filippou
Inorganics 2023, 11(3), 129; https://doi.org/10.3390/inorganics11030129 - 18 Mar 2023
Cited by 5 | Viewed by 1680
Abstract
We report a broad theoretical study on [(PMe3)3MER]+ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = ArMes, Tbb, (ArMes = 2,6-dimesitylphenyl; Tbb = C6H [...] Read more.
We report a broad theoretical study on [(PMe3)3MER]+ complexes, with M = Ni, Pd, Pt, E = C, Si, Ge, Sn, Pb, and R = ArMes, Tbb, (ArMes = 2,6-dimesitylphenyl; Tbb = C6H2-2,6-[CH(SiMe3)2]2-4-tBu). A few years ago, our group succeeded in obtaining heavier homologues of cationic group 10 carbyne complexes via halide abstraction of the tetrylidene complexes [(PMe3)3M=E(X)R] (X = Cl, Br) using a halide scavenger. The electronic structure and the M-E bonds of the [(PMe3)3MER]+ complexes were analyzed utilizing quantum-chemical tools, such as the Pipek–Mezey orbital localization method, the energy decomposition analysis (EDA), and the extended-transition state method with natural orbitals of chemical valence (ETS-NOCV). The carbyne, silylidyne complexes, and the germylidyne complex [(PMe3)3NiGeArMes]+ are suggested to be tetrylidyne complexes featuring donor–acceptor metal tetrel triple bonds, which are composed of two strong π(M→E) and one weaker σ(E→M) interaction. In comparison, the complexes with M = Pd, Pt; E = Sn, Pb; and R = ArMes are best described as metallotetrylenes and exhibit considerable M−E−C bending, a strong σ(M→E) bond, weakened M−E π-components, and lone pair density at the tetrel atoms. Furthermore, bond cleavage energy (BCE) and bond dissociation energy (BDE) reveal preferred splitting into [M(PMe3)3]+ and [ER] fragments for most complex cations in the range of 293.3–618.3 kJ·mol−1 and 230.4–461.6 kJ·mol−1, respectively. Finally, an extensive study of the potential energy hypersurface varying the M−E−C angle indicates the presence of isomers with M−E−C bond angles of around 95°. Interestingly, these isomers are energetically favored for M = Pd, Pt; E = Sn, Pb; and R = ArMes over the less-bent structures by 13–29 kJ·mol−1. Full article
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13 pages, 12547 KiB  
Article
Operando CO Infrared Spectroscopy and On-Line Mass Spectrometry for Studying the Active Phase of IrO2 in the Catalytic CO Oxidation Reaction
by Phillip Timmer, Tim Weber, Lorena Glatthaar and Herbert Over
Inorganics 2023, 11(3), 102; https://doi.org/10.3390/inorganics11030102 - 28 Feb 2023
Cited by 3 | Viewed by 1288
Abstract
We combine operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with on-line mass spectrometry (MS) to study the correlation between the oxidation state of titania-supported IrO2 catalysts (IrO2@TiO2) and their catalytic activity in the prototypical CO oxidation reaction. [...] Read more.
We combine operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with on-line mass spectrometry (MS) to study the correlation between the oxidation state of titania-supported IrO2 catalysts (IrO2@TiO2) and their catalytic activity in the prototypical CO oxidation reaction. Here, the stretching vibration of adsorbed COad serves as the probe. DRIFTS provides information on both surface and gas phase species. Partially reduced IrO2 is shown to be significantly more active than its fully oxidized counterpart, with onset and full conversion temperatures being about 50 °C lower for reduced IrO2. By operando DRIFTS, this increase in activity is traced to a partially reduced state of the catalysts, as evidenced by a broad IR band of adsorbed CO reaching from 2080 to 1800 cm−1. Full article
(This article belongs to the Special Issue Recent Advancements of Metal Oxide in Catalysis)
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11 pages, 1564 KiB  
Article
Synthesis of Novel Multifunctional bora-Ibuprofen Derivatives
by Randika T. Abeysinghe, Alexis C. Ravenscroft, Steven W. Knowlden, Novruz G. Akhmedov, Brian S. Dolinar and Brian V. Popp
Inorganics 2023, 11(2), 70; https://doi.org/10.3390/inorganics11020070 - 02 Feb 2023
Cited by 3 | Viewed by 2635
Abstract
A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO2 and B2pin2 reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions [...] Read more.
A unique class of β-boron-functionalized non-steroidal anti-inflammatory compound (pinB-NSAID) was previously synthesized via copper-catalyzed 1,2-difunctionalization of the respective vinyl arene with CO2 and B2pin2 reagents. Here, pinacolylboron-functionalized ibuprofen (pinB-ibuprofen) was used as a model substrate to develop the conditions for pinacol deprotection and subsequent boron functionalization. Initial pinacol-boronic ester deprotection was achieved by transesterification with diethanolamine (DEA) from the boralactonate organic salt. The resulting DEA boronate adopts a spirocyclic boralactonate structure rather than a diazaborocane–DABO boronate structure. The subsequent acid-mediated hydrolysis of DEA and transesterification/transamination provided a diverse scope of new boron-containing ibuprofen derivatives. Full article
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19 pages, 6775 KiB  
Article
Coordination Chemistry of Polynitriles, Part XII—Serendipitous Synthesis of the Octacyanofulvalenediide Dianion and Study of Its Coordination Chemistry with K+ and Ag+
by Patrick Nimax, Yannick Kunzelmann and Karlheinz Sünkel
Inorganics 2023, 11(2), 71; https://doi.org/10.3390/inorganics11020071 - 02 Feb 2023
Cited by 1 | Viewed by 1147
Abstract
The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] ( [...] Read more.
The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] (5), which can be transformed via reaction with AgNO3 to the corresponding Ag+ salt (4), which in turn can be reacted with KCl to yield the corresponding K+ salt 6. The molecular and crystal structures of 46 could be determined, and show a significantly twisted aromatic dianion which uses all its nitrile groups for coordination to the metals; 4 and 6 form three-dimensional coordination polymers with fourfold coordinated Ag+ and eightfold coordinated K+ cations. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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18 pages, 3303 KiB  
Article
Interactions of an Artificial Zinc Finger Protein with Cd(II) and Hg(II): Competition and Metal and DNA Binding
by Bálint Hajdu, Éva Hunyadi-Gulyás and Béla Gyurcsik
Inorganics 2023, 11(2), 64; https://doi.org/10.3390/inorganics11020064 - 29 Jan 2023
Cited by 2 | Viewed by 1867
Abstract
Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as [...] Read more.
Cys2His2 zinc finger proteins are important for living organisms, as they—among other functions—specifically recognise DNA when Zn(II) is coordinated to the proteins, stabilising their ββα secondary structure. Therefore, competition with other metal ions may alter their original function. Toxic metal ions such as Cd(II) or Hg(II) might be especially dangerous because of their similar chemical properties to Zn(II). Most competition studies carried out so far have involved small zinc finger peptides. Therefore, we have investigated the interactions of toxic metal ions with a zinc finger proteins consisting of three finger units and the consequences on the DNA binding properties of the protein. Binding of one Cd(II) per finger subunit of the protein was shown by circular dichroism spectroscopy, fluorimetry and electrospray ionisation mass spectrometry. Cd(II) stabilised a similar secondary structure to that of the Zn(II)-bound protein but with a slightly lower affinity. In contrast, Hg(II) could displace Zn(II) quantitatively (logβ′ ≥ 16.7), demolishing the secondary structure, and further Hg(II) binding was also observed. Based on electrophoretic gel mobility shift assays, the Cd(II)-bound zinc finger protein could recognise the specific DNA target sequence similarly to the Zn(II)-loaded form but with a ~0.6 log units lower stability constant, while Hg(II) could destroy DNA binding completely. Full article
(This article belongs to the Special Issue Recent Progress in Coordination Chemistry)
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21 pages, 5621 KiB  
Review
The Applications of Metallacycles and Metallacages
by Changfeng Yin, Jiaxing Du, Bogdan Olenyuk, Peter J. Stang and Yan Sun
Inorganics 2023, 11(2), 54; https://doi.org/10.3390/inorganics11020054 - 22 Jan 2023
Cited by 6 | Viewed by 1925
Abstract
Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and [...] Read more.
Metallacycles and metallacages constitute a class of coordination compounds composed of metal ions and organic ligands. Because of their precise stoichiometry, the flexibility and viability of design, metallacycles and metallacages have attracted considerable attention as supramolecular assemblies. Various two-dimensional polygons, three-dimensional polyhedra, and other nanoscale materials have been constructed and applied. The highly diverse structures, sizes, and shapes endow metallacycles and metallacages with unique physical and chemical properties and make them suitable for various applications such as encapsulation, separation, catalysis, and biological science. Herein, we review the recent developments in various metallacycles and metallacages in different fields. The text highlights biomedical applications involving molecular recognition and binding, antibacterial activity, and especially cancer diagnosis and treatment, including imaging, chemotherapy, PDT, and PTT. Full article
(This article belongs to the Special Issue Metallamacrocycles and Metallacages: Foundations and Applications)
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12 pages, 3788 KiB  
Article
The Influence of Different Recombination Pathways on Hysteresis in Perovskite Solar Cells with Ion Migration
by Biao Li, Kun Chen, Pengjie Hang, Yuxin Yao, Chenxia Kan, Zechen Hu, Ying Wang, Yiqiang Zhang, Deren Yang and Xuegong Yu
Inorganics 2023, 11(2), 52; https://doi.org/10.3390/inorganics11020052 - 19 Jan 2023
Viewed by 1441
Abstract
The impact of hysteresis on the power conversion efficiency (PCE) of perovskite solar cells (PSCs) still faces uncertainties despite the rapid development of perovskite photovoltaics. Although ion migration in perovskites is regarded as the chief culprit for hysteresis, charge carrier recombination pathways in [...] Read more.
The impact of hysteresis on the power conversion efficiency (PCE) of perovskite solar cells (PSCs) still faces uncertainties despite the rapid development of perovskite photovoltaics. Although ion migration in perovskites is regarded as the chief culprit for hysteresis, charge carrier recombination pathways in PSCs are proposed to be necessary for the occurrence of hysteresis. Here, the impact of both bulk recombination and interface recombination on hysteresis in PSCs is investigated via drift–diffusion modeling. The simulation results demonstrate a direct correlation between recombination pathways and hysteresis in PSCs with ion migration. The simulation reveals that recombination pathways in PSCs will react to the variation in charge carrier distribution under different voltage scanning directions induced by ion migration in absorber layers, which leads to hysteresis in PSCs. Moreover, the hysteresis in normal (N-I-P) PSCs with different electron transport layers (ETLs) including sintered SnO2, SnO2 nano crystals and TiO2 is experimentally explored. The results demonstrate that multiple recombination pathways coupled with ion migration can lead to obvious hysteresis in fabricated PSCs which is consistent with simulation results. This work provides great insight into hysteresis management upon composition, additive and interface engineering in PSCs. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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18 pages, 4081 KiB  
Article
Latonduine-1-Amino-Hydantoin Hybrid, Triazole-Fused Latonduine Schiff Bases and Their Metal Complexes: Synthesis, X-ray and Electron Diffraction, Molecular Docking Studies and Antiproliferative Activity
by Christopher Wittmann, Tim Gruene, Alexander Prado-Roller, Sandra Aranđelović, Jóhannes Reynisson and Vladimir B. Arion
Inorganics 2023, 11(1), 30; https://doi.org/10.3390/inorganics11010030 - 03 Jan 2023
Cited by 3 | Viewed by 1755
Abstract
A series of latonduine derivatives, namely 11-nitro-indolo[2,3-d]benzazepine-7-(1-amino-hydantoin) (B), triazole-fused indolo[2,3-d]benzazepine-based Schiff bases HL1 and HL2 and metal complexes [M(p-cymene)(HL1)Cl]Cl, where M = Ru (1), Os (2), and [...] Read more.
A series of latonduine derivatives, namely 11-nitro-indolo[2,3-d]benzazepine-7-(1-amino-hydantoin) (B), triazole-fused indolo[2,3-d]benzazepine-based Schiff bases HL1 and HL2 and metal complexes [M(p-cymene)(HL1)Cl]Cl, where M = Ru (1), Os (2), and [Cu(HL2)Cl2] (3) were synthesized and characterized by spectroscopic techniques (UV–vis, 1H, 13C, 15N–1H HSQC NMR) and ESI mass spectrometry. The molecular structures of B and HL1 were confirmed by single-crystal X-ray diffraction, while that of 3 by electron diffraction of nanometer size crystalline sample. Molecular docking calculations of species B in the binding pocket of PIM-1 enzyme revealed that the 1-amino-hydantoin moiety is not involved in any hydrogen-bonding interactions, even though a good accommodation of the host molecule in the ATP binding pocket of the enzyme was found. The antiproliferative activity of organic compounds B, HL1 and HL2, as well as complexes 13 was investigated in lung adenocarcinoma A549, colon adenocarcinoma LS-174 and triple-negative breast adenocarcinoma MDA-MB-231 cells and normal human lung fibroblast cells MRC-5 by MTT assays; then, the results are discussed. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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16 pages, 4686 KiB  
Article
The Crystal Structure of Carbonic Acid
by Sebastian Benz, Da Chen, Andreas Möller, Michael Hofmann, David Schnieders and Richard Dronskowski
Inorganics 2022, 10(9), 132; https://doi.org/10.3390/inorganics10090132 - 03 Sep 2022
Cited by 3 | Viewed by 7812
Abstract
Ubiquitous carbonic acid, H2CO3, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is known from a plethora of physicochemical studies. Its crystal structure has now been determined from neutron-diffraction data on a deuterated sample in a specially [...] Read more.
Ubiquitous carbonic acid, H2CO3, a key molecule in biochemistry, geochemistry, and also extraterrestrial chemistry, is known from a plethora of physicochemical studies. Its crystal structure has now been determined from neutron-diffraction data on a deuterated sample in a specially built hybrid clamped cell. At 1.85 GPa, D2CO3 crystallizes in the monoclinic space group P21/c with a = 5.392(2), b = 6.661(4), c = 5.690(1) Å, β = 92.66(3)°, Z = 4, with one symmetry-inequivalent anti-anti shaped D2CO3 molecule forming dimers, as previously predicted. Quantum chemistry evidences π bonding within the CO3 molecular core, very strong hydrogen bonding between the molecules, and a massive influence of the crystal field on all bonds; phonon calculations emphasize the locality of the vibrations, being rather insensitive to the extended structure. Full article
(This article belongs to the Special Issue Inorganics: 10th Anniversary)
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8 pages, 1787 KiB  
Article
A Partial Anion Disorder in SrVO2H Induced by Biaxial Tensile Strain
by Morito Namba, Hiroshi Takatsu, Wataru Yoshimune, Aurélien Daniel, Shoichi Itoh, Takahito Terashima and Hiroshi Kageyama
Inorganics 2020, 8(4), 26; https://doi.org/10.3390/inorganics8040026 - 08 Apr 2020
Cited by 13 | Viewed by 4960
Abstract
SrVO2H, obtained by a topochemical reaction of SrVO3 perovskite using CaH2, is an anion-ordered phase with hydride anions exclusively at the apical site. In this study, we conducted a CaH2 reduction of SrVO3 thin films epitaxially [...] Read more.
SrVO2H, obtained by a topochemical reaction of SrVO3 perovskite using CaH2, is an anion-ordered phase with hydride anions exclusively at the apical site. In this study, we conducted a CaH2 reduction of SrVO3 thin films epitaxially grown on KTaO3 (KTO) substrates. When reacted at 530 °C for 12 h, we observed an intermediate phase characterized by a smaller tetragonality of c/a = 0.96 (vs. c/a = 0.93 for SrVO2H), while a longer reaction of 24 h resulted in the known phase of SrVO2H. This fact suggests that the intermediate phase is a metastable state stabilized by applying tensile strain from the KTO substrate (1.4%). In addition, secondary ion mass spectrometry (SIMS) revealed that the intermediate phase has a hydrogen content close to that of SrVO2H, suggesting a partially disordered anion arrangement. Such kinetic trapping of an intermediate state by biaxial epitaxial strain not only helps to acquire a new state of matter but also advances our understanding of topochemical reaction processes in extended solids. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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11 pages, 5648 KiB  
Communication
Magnetic Composite Submicron Carriers with Structure-Dependent MRI Contrast
by Anastasiia A. Kozlova, Sergey V. German, Vsevolod S. Atkin, Victor V. Zyev, Maxwell A. Astle, Daniil N. Bratashov, Yulia I. Svenskaya and Dmitry A. Gorin
Inorganics 2020, 8(2), 11; https://doi.org/10.3390/inorganics8020011 - 30 Jan 2020
Cited by 18 | Viewed by 3233
Abstract
Magnetic contrast agents are widely used in magnetic resonance imaging in order to significantly change the signals from the regions of interest in comparison with the surrounding tissue. Despite a high variety of single-mode T1 or T2 contrast agents, there is [...] Read more.
Magnetic contrast agents are widely used in magnetic resonance imaging in order to significantly change the signals from the regions of interest in comparison with the surrounding tissue. Despite a high variety of single-mode T1 or T2 contrast agents, there is a need for dual-mode contrast from the one agent. Here, we report on the synthesis of magnetic submicron carriers, containing Fe3O4 nanoparticles in their structure. We show the ability to control magnetic resonance contrast by changing not only the number of magnetite nanoparticles in one carrier or the concentration of magnetite in the suspension but also the structure of the core–shell itself. The obtained data open up the prospects for dual-mode T1/T2 magnetic contrast formation, as well as provides the basis for future investigations in this direction. Full article
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59 pages, 11275 KiB  
Review
Magnetic Materials and Systems: Domain Structure Visualization and Other Characterization Techniques for the Application in the Materials Science and Biomedicine
by Roberto Nisticò, Federico Cesano and Francesca Garello
Inorganics 2020, 8(1), 6; https://doi.org/10.3390/inorganics8010006 - 17 Jan 2020
Cited by 43 | Viewed by 12615
Abstract
Magnetic structures have attracted a great interest due to their multiple applications, from physics to biomedicine. Several techniques are currently employed to investigate magnetic characteristics and other physicochemical properties of magnetic structures. The major objective of this review is to summarize the current [...] Read more.
Magnetic structures have attracted a great interest due to their multiple applications, from physics to biomedicine. Several techniques are currently employed to investigate magnetic characteristics and other physicochemical properties of magnetic structures. The major objective of this review is to summarize the current knowledge on the usage, advances, advantages, and disadvantages of a large number of techniques that are currently available to characterize magnetic systems. The present review, aiming at helping in the choice of the most suitable method as appropriate, is divided into three sections dedicated to characterization techniques. Firstly, the magnetism and magnetization (hysteresis) techniques are introduced. Secondly, the visualization methods of the domain structures by means of different probes are illustrated. Lastly, the characterization of magnetic nanosystems in view of possible biomedical applications is discussed, including the exploitation of magnetism in imaging for cell tracking/visualization of pathological alterations in living systems (mainly by magnetic resonance imaging, MRI). Full article
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63 pages, 14258 KiB  
Review
Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood
by Pradeep R. Varadwaj, Arpita Varadwaj and Helder M. Marques
Inorganics 2019, 7(3), 40; https://doi.org/10.3390/inorganics7030040 - 12 Mar 2019
Cited by 114 | Viewed by 8097
Abstract
In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions [...] Read more.
In addition to the underlying basic concepts and early recognition of halogen bonding, this paper reviews the conflicting views that consistently appear in the area of noncovalent interactions and the ability of covalently bonded halogen atoms in molecules to participate in noncovalent interactions that contribute to packing in the solid-state. It may be relatively straightforward to identify Type-II halogen bonding between atoms using the conceptual framework of σ-hole theory, especially when the interaction is linear and is formed between the axial positive region (σ-hole) on the halogen in one monomer and a negative site on a second interacting monomer. A σ-hole is an electron density deficient region on the halogen atom X opposite to the R–X covalent bond, where R is the remainder part of the molecule. However, it is not trivial to do so when secondary interactions are involved as the directionality of the interaction is significantly affected. We show, by providing some specific examples, that halogen bonds do not always follow the strict Type-II topology, and the occurrence of Type-I and -III halogen-centered contacts in crystals is very difficult to predict. In many instances, Type-I halogen-centered contacts appear simultaneously with Type-II halogen bonds. We employed the Independent Gradient Model, a recently proposed electron density approach for probing strong and weak interactions in molecular domains, to show that this is a very useful tool in unraveling the chemistry of halogen-assisted noncovalent interactions, especially in the weak bonding regime. Wherever possible, we have attempted to connect some of these results with those reported previously. Though useful for studying interactions of reasonable strength, IUPAC’s proposed “less than the sum of the van der Waals radii” criterion should not always be assumed as a necessary and sufficient feature to reveal weakly bound interactions, since in many crystals the attractive interaction happens to occur between the midpoint of a bond, or the junction region, and a positive or negative site. Full article
(This article belongs to the Special Issue Halogen Bonding: Fundamentals and Applications)
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15 pages, 591 KiB  
Review
Designing Ruthenium Anticancer Drugs: What Have We Learnt from the Key Drug Candidates?
by James P. C. Coverdale, Thaisa Laroiya-McCarron and Isolda Romero-Canelón
Inorganics 2019, 7(3), 31; https://doi.org/10.3390/inorganics7030031 - 01 Mar 2019
Cited by 127 | Viewed by 8779
Abstract
After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro [...] Read more.
After nearly 20 years of research on the use of ruthenium in the fight against cancer, only two Ru(III) coordination complexes have advanced to clinical trials. During this time, the field has produced excellent candidate drugs with outstanding in vivo and in vitro activity; however, we have yet to find a ruthenium complex that would be a viable alternative to platinum drugs currently used in the clinic. We aimed to explore what we have learned from the most prominent complexes in the area, and to challenge new concepts in chemical design. Particularly relevant are studies involving NKP1339, NAMI-A, RM175, and RAPTA-C, which have paved the way for current research. We explored the development of the ruthenium anticancer field considering that the mechanism of action of complexes no longer focuses solely on DNA interactions, but explores a diverse range of cellular targets involving multiple chemical strategies. Full article
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14 pages, 7701 KiB  
Article
Development and Validation of Liquid Chromatography-Based Methods to Assess the Lipophilicity of Cytotoxic Platinum(IV) Complexes
by Matthias H. M. Klose, Sarah Theiner, Hristo P. Varbanov, Doris Hoefer, Verena Pichler, Mathea Sophia Galanski, Samuel M. Meier-Menches and Bernhard K. Keppler
Inorganics 2018, 6(4), 130; https://doi.org/10.3390/inorganics6040130 - 04 Dec 2018
Cited by 29 | Viewed by 6366
Abstract
Lipophilicity is a crucial parameter for drug discovery, usually determined by the logarithmic partition coefficient (Log P) between octanol and water. However, the available detection methods have restricted the widespread use of the partition coefficient in inorganic medicinal chemistry, and recent investigations have [...] Read more.
Lipophilicity is a crucial parameter for drug discovery, usually determined by the logarithmic partition coefficient (Log P) between octanol and water. However, the available detection methods have restricted the widespread use of the partition coefficient in inorganic medicinal chemistry, and recent investigations have shifted towards chromatographic lipophilicity parameters, frequently without a conversion to derive Log P. As high-performance liquid chromatography (HPLC) instruments are readily available to research groups, a HPLC-based method is presented and validated to derive the partition coefficient of a set of 19 structurally diverse and cytotoxic platinum(IV) complexes exhibiting a dynamic range of at least four orders of magnitude. The chromatographic lipophilicity parameters φ0 and Log kw were experimentally determined for the same set of compounds, and a correlation was obtained that allows interconversion between the two lipophilicity scales, which was applied to an additional set of 34 platinum(IV) drug candidates. Thereby, a φ0 = 58 corresponds to Log P = 0. The same approaches were successfully evaluated to determine the distribution coefficient (Log D) of five ionisable platinum(IV) compounds to sample pH-dependent effects on the lipophilicity. This study provides straight-forward HPLC-based methods to determine the lipophilicity of cytotoxic platinum(IV) complexes in the form of Log P and φ0 that can be interconverted and easily expanded to other metal-based compound classes. Full article
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14 pages, 1967 KiB  
Article
S–H Bond Activation in Hydrogen Sulfide by NHC-Stabilized Silyliumylidene Ions
by Amelie Porzelt, Julia I. Schweizer, Ramona Baierl, Philipp J. Altmann, Max C. Holthausen and Shigeyoshi Inoue
Inorganics 2018, 6(2), 54; https://doi.org/10.3390/inorganics6020054 - 24 May 2018
Cited by 16 | Viewed by 5520
Abstract
Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S–H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes2-C6H3, Mes = [...] Read more.
Reactivity studies of silyliumylidenes remain scarce with only a handful of publications to date. Herein we report the activation of S–H bonds in hydrogen sulfide by mTer-silyliumylidene ion A (mTer = 2,6-Mes2-C6H3, Mes = 2,4,6-Me3-C6H2) to yield an NHC-stabilized thiosilaaldehyde B. The results of NBO and QTAIM analyses suggest a zwitterionic formulation of the product B as the most appropriate. Detailed mechanistic investigations are performed at the M06-L/6-311+G(d,p)(SMD: acetonitrile/benzene)//M06-L/6-311+G(d,p) level of density functional theory. Several pathways for the formation of thiosilaaldehyde B are examined. The energetically preferred route commences with a stepwise addition of H2S to the nucleophilic silicon center. Subsequent NHC dissociation and proton abstraction yields the thiosilaaldehyde in a strongly exergonic reaction. Intermediacy of a chlorosilylene or a thiosilylene is kinetically precluded. With an overall activation barrier of 15 kcal/mol, the resulting mechanistic picture is fully in line with the experimental observation of an instantaneous reaction at sub-zero temperatures. Full article
(This article belongs to the Special Issue Coordination Chemistry of Silicon)
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34 pages, 10625 KiB  
Review
Ruthenium Complexes as Sensitizers in Dye-Sensitized Solar Cells
by Sadig Aghazada and Mohammad Khaja Nazeeruddin
Inorganics 2018, 6(2), 52; https://doi.org/10.3390/inorganics6020052 - 21 May 2018
Cited by 97 | Viewed by 10195
Abstract
In this review, we discuss the main directions in which ruthenium complexes for dye-sensitized solar cells (DSCs) were developed. We critically discuss the implemented design principles. This review might be helpful at this moment when a breakthrough is needed for DSC technology to [...] Read more.
In this review, we discuss the main directions in which ruthenium complexes for dye-sensitized solar cells (DSCs) were developed. We critically discuss the implemented design principles. This review might be helpful at this moment when a breakthrough is needed for DSC technology to prove its market value. Full article
(This article belongs to the Collection Coordination Complexes for Dye-Sensitized Solar Cells (DSCs))
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