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13 pages, 3170 KiB

Open AccessArticle

A New 3D Iodoargentate Hybrid: Structure, Optical/Photoelectric Performance and Theoretical Research

by Jun Li, Shuyue Xie, Ming Pang, Jiacheng Zhu, Jinting Wu, Yongdi Zhang and Bo Zhang

Molecules 2023, 28(24), 8033; https://doi.org/10.3390/molecules28248033 - 10 Dec 2023

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The explorations of new three-dimensional (3D) microporous metal halides, especially the iodoargentate-based hybrids, and understanding of their structure-activity relationships are still quite essential but full of great challenges. Herein, with the aromatic 4,4′-dpa (4,4′-dpa = 4,4′-dipyridylamine) ligands as the structural directing agents, we [...] Read more.

The explorations of new three-dimensional (3D) microporous metal halides, especially the iodoargentate-based hybrids, and understanding of their structure-activity relationships are still quite essential but full of great challenges. Herein, with the aromatic 4,4′-dpa (4,4′-dpa = 4,4′-dipyridylamine) ligands as the structural directing agents, we solvothermal synthesized and structurally characterized a novel member of microporous iodoargentate family, namely [H₂-4,4′-dpa]Ag₆I₈ (1). Compound 1 possesses a unique and complicated 3D [Ag₆I₈]_n²ⁿ⁻ anionic architecture that was built up from the unusual hexameric [Ag₆I₁₃] secondary building units (SBUs). Research on optical properties indicated that compound 1 exhibited semiconductor behavior, with an optical band gap of 2.50 eV. Under the alternate irradiation of light, prominent photoelectric switching abilities could be achieved by compound [H₂-4,4′-dpa]Ag₆I₈, whose photocurrent densities (0.37 μA·cm⁻² for visible light and 1.23 μA·cm⁻² for full-spectrum) compared well with or exceeded those of some high-performance halide counterparts. Further theoretical calculations revealed that the relatively dispersed conduction bands (CBs) structures in compound 1 induced higher electron mobilities, which may be responsible for its good photoelectricity. Presented in this work also comprised the analyses of Hirshfeld surface, powder X-ray diffractometer (PXRD), thermogravimetric measurement, energy-dispersive X-ray spectrum (EDX) along with X-ray photoelectron spectroscopy (XPS). Full article

(This article belongs to the Special Issue Metal Coordination Compounds: Synthesis, Electronic Structure, Properties and Application)

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29 pages, 6328 KiB

Open AccessArticle

Gold-Based Coronands as Hosts for M³⁺ Metal Ions: Ring Size Matters

by Suelen Ferreira Sucena, Türkan Ilgin Demirer, Anna Baitullina, Adelheid Hagenbach, Jacqueline Grewe, Sarah Spreckelmeyer, Juliane März, Astrid Barkleit, Pedro Ivo da Silva Maia, Hung Huy Nguyen and Ulrich Abram

Molecules 2023, 28(14), 5421; https://doi.org/10.3390/molecules28145421 - 14 Jul 2023

Cited by 2 | Viewed by 1401

Abstract

The controlled, self-assembled synthesis of multinuclear coordination compounds can be performed via different approaches. Frequently, steric, geometric and/or electronic factors located at the ligand systems predefine the way in which metal ions can assemble them to large aggregates. For the compounds in the [...] Read more.

The controlled, self-assembled synthesis of multinuclear coordination compounds can be performed via different approaches. Frequently, steric, geometric and/or electronic factors located at the ligand systems predefine the way in which metal ions can assemble them to large aggregates. For the compounds in the present paper, also the Pearson’s acidities and preferred coordination geometries of the metal ions were used as organization principles. The ligand under study, 2,6-dipicolinoylbis(N,N-diethylthiourea), H₂L1^ethyl, possesses ‘soft’ sulfur and ‘hard’ nitrogen and oxygen donors. One-pot reactions of this compound with [AuCl(tht)] (tht = tetrahydrothiophene) and M³⁺ salts (M = Sc, Y, La, Ln, Ga, In) give products with gold-based {Au₃(L1^ethyl)₃}³⁺ or {Au₂(L1^ethyl)₂}²⁺ coronands, which host central M³⁺ ions. The formation of such units is templated by the M³⁺ ions and the individual size of the coronand rings is dependent on the ionic radii of the central ions in a way that small ions such as Ga³⁺ form a [Ga⊂{Au₂(L1^ethyl)₂}]⁺ assembly, while larger ions (starting from Sc³⁺/In³⁺) establish neutral [M⊂{Au₃(L1^ethyl)₃}] units with nine-coordinate central ions. Full article

(This article belongs to the Special Issue Metal Coordination Compounds: Synthesis, Electronic Structure, Properties and Application)

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14 pages, 3511 KiB

Open AccessFeature PaperArticle

The Dichotomy of Mn–H Bond Cleavage and Kinetic Hydricity of Tricarbonyl Manganese Hydride Complexes

by Elena S. Osipova, Sergey A. Kovalenko, Ekaterina S. Gulyaeva, Nikolay V. Kireev, Alexander A. Pavlov, Oleg A. Filippov, Anastasia A. Danshina, Dmitry A. Valyaev, Yves Canac, Elena S. Shubina and Natalia V. Belkova

Molecules 2023, 28(8), 3368; https://doi.org/10.3390/molecules28083368 - 11 Apr 2023

Cited by 4 | Viewed by 1602

Abstract

Acid-base characteristics (acidity, pKa, and hydricity, ΔG°_H− or k_H−) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M–H bond may change radically at the stage of [...] Read more.

Acid-base characteristics (acidity, pKa, and hydricity, ΔG°_H− or k_H−) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M–H bond may change radically at the stage of formation of a non-covalent adduct with an acidic/basic partner. This stage is responsible for subsequent hydrogen ion (hydride or proton) transfer. Here, the reaction of tricarbonyl manganese hydrides mer,trans–[L₂Mn(CO)₃H] (1; L = P(OPh)₃, 2; L = PPh₃) and fac–[(L–L′)Mn(CO)₃H] (3, L–L′ = Ph₂PCH₂PPh₂ (dppm); 4, L–L′ = Ph₂PCH₂–NHC) with organic bases and Lewis acid (B(C₆F₅)₃) was explored by spectroscopic (IR, NMR) methods to find the conditions for the Mn–H bond repolarization. Complex 1, bearing phosphite ligands, features acidic properties (pKa 21.3) but can serve also as a hydride donor (ΔG^≠_298K = 19.8 kcal/mol). Complex 3 with pronounced hydride character can be deprotonated with KHMDS at the CH₂–bridge position in THF and at the Mn–H position in MeCN. The kinetic hydricity of manganese complexes 1–4 increases in the order mer,trans–[(P(OPh)₃)₂Mn(CO)₃H] (1) < mer,trans–[(PPh₃)₂Mn(CO)₃H] (2) ≈ fac–[(dppm)Mn(CO)₃H] (3) < fac–[(Ph₂PCH₂NHC)Mn(CO)₃H] (4), corresponding to the gain of the phosphorus ligand electron-donor properties. Full article

(This article belongs to the Special Issue Metal Coordination Compounds: Synthesis, Electronic Structure, Properties and Application)

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