Ашық рұқсат
Рұқсат берілді
Тек жазылушылар үшін
Том 50, № 9 (2024)
Articles
Development of the Cluster Chemistry, Supramolecular Chemistry and Chemistry of Metal-Organic Frameworks by Professor Vladimir P. Fedin and His School
Аннотация
The article briefly summarizes the main scientific directions contributed to and developed by the outstanding scientist—a leader in the field of coordination chemistry, cluster chemistry, supramolecular chemistry and chemistry of metal-organic coordination polymers, Corresponding Member of the Russian Academy of Sciences Vladimir Petrovich Fedin.
535-543
3,6-Dipyridyl-1,2,4,5-tetrazine in the Synthesis of Zinc and Cadmium Metal-Organic Frameworks with Anilate-Type Ligands
Аннотация
New heteroleptic metal-organic frameworks (MOF) of zinc (3D MOF) and cadmium (2D MOF) are prepared by the two-stage synthesis: [Zn(pQ)(DPT)]·2DMF (I) and Cd2(NO3)2-(pQ)(DPT)3]·2DMF·2MeOH (II), where pQ is the 2,5-dihydroxy-3,6-di-tert-butyl-para-benzoquinone dianion, DPT is 3,6-di(pyridin-4-yl)-1,2,4,5-tetrazine, and DMF is N,N-dimethylformamide (DMF). The structures of the compounds are studied by XRD (CIF files CCDC nos. 2332754 (I) and 2332755 (II)). The thermal stability of the MOF is studied by thermogravimetry.
544-556
Scalable Approach for Grafting Qubit Candidates onto The Surface of MOF-808 Framework
Аннотация
The development of quantum bits (qubits) is crucial for the progress of quantum technologies. Among various approaches, the qubits based on paramagnetic centers have decent advantages, including their diversity and possibilities of regular ordering, for example, within the structure of metal-organic frameworks (MOFs). In the present work a simple and scalable approach to obtain qubit candidates based on stable organic radical 3-carboxy-proxyl and MOF-808 framework has been demonstrated. Investigation of the obtained compounds with different radical amounts using electron paramagnetic resonance (EPR) demonstrates the presence of two fractions of radicals, which is supported by simulations. Sufficiently long phase memory time at room temperature for the radicals adsorbed into MOF (0.39 μs), as well as the observed Rabi nutations, allow considering this material as a platform for qubits design. The developed approach is capable of incorporating various amounts of paramagnetic centers into the MOF structure and can be employed to obtain other spin qubit candidates.
557-565
Cadmium(II)-Organic Frameworks with the Polynuclear Unit: Dimensionality Control and Luminescence Response to Pyridine
Аннотация
New porous metal-organic frameworks (MOF) [Cd7(Btdc)7(Bpa)2(Dmf)2(H2O)2] · 15Dmf · 2H2O (I) and [Cd7(Btdc)7(Bpe)2(Dmf)2] · 15Dmf · 3H2O (II) (H2Btdc is 2,2’-bithiophene-5,5’-dicarboxylic acid, Bpa is 1,2-bis(4-pyridyl)ethane, Bpe is 1,2-bis(4-pyridyl)ethylene, and Dmf is N,N-dimethylformamide) are synthesized under solvatothermal conditions. The structures and compositions of the compounds are determined by single-crystal X-ray diffraction (XRD) (CIF files ССDС nos. 2364290 (I) and 2364289 (II)) and confirmed by powder XRD, elemental analysis, thermogravimetry, and IR spectroscopy. Compound I has a 2D structure based on the heptanuclear discrete building unit {Cd7} with the linear structure. Compound II is a 3D MOF in which the {Cd7} building units are linked into a continuous chain motif due to additional interactions. The formation of discrete or continuous chains is directly related to the nature of the N-donor bridging ligand (Bpe or Bpa). Compounds I and II have open structures with the accessible volume about 50%. The solvate molecules are replaced by thiophene, benzene, and pyridine, and the luminescence properties of the prepared adducts are studied. Luminescence quenching in the presence of thiophene and an increase in the luminescence intensity in the presence of pyridine accompanied by a change in the quantum yield by 4–5 times are shown.
566-576
Metal-Organic Frameworks of Cobalt(II) with 4,7-Di(1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole and Aromatic Dicarboxylic Acids: Synthesis, Crystal Structures, and Magnetic Properties
Аннотация
The reactions of cobalt(II) nitrate with 4,7-di(1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole (Tr2btd) and aromatic dicarboxylic acids (terephthalic (H2bdc), 2,6-naphthalenedicarboxylic (2,6-H2Ndc), and 2,5-furandicarboxylic (2,5-H2Fdc) acids) afford metal-organic frameworks [Co(Tr2btd)(bdc)]n (I) and {[Co2(Tr2btd)(Dmf)(2,6-Ndc)2]·Dmf}n (II) with the layered structures and chain metal-organic framework [Co(Tr2btd)2(H2O)(2,5-Fdc)]n (III). Compounds I and III are paramagnetic in a temperature range of 1.77–300 K without exchange interactions between the Co2+ cations, and compound II exhibits the antiferromagnetic interaction between the Co2+ cations in the binuclear building blocks with the exchange interaction constant J ≈ −100 K. Single crystals of the phase of compound IIIa with the identical composition but different structure are found when taking samples for X-ray diffraction (XRD) analysis. The molecular structures of metal-organic frameworks I, II, III, and IIIa are determined by XRD (CIF files CCDC nos. 2343141 (I), 2343297 (II), 2343296 (III), and 2343140 (IIIa)).
577-591
Neutral Terbium(III) Tris(complex) with 4,4,5,5,6,6,6-Heptafluoro-1-(1-methyl-1H-pyrazol-4-yl)hexane-1,3-dione: Synthesis, Structure, and Spectral Luminescence Properties
Аннотация
The reaction of 1,3-diketone containing 1-methyl-1H-pyrazol-4-yl and perfluoropropyl fragments with TbCl3·6H2O in the presence of NaOH in ethanol is studied. The molecular and crystal structures of the complex are studied by single-crystal X-ray diffraction (XRD). Compound [Tb(L)3(EtOH)2] crystallizes in the triclinic crystal system with the space group. The geometry of the coordination polyhedron {LnO8} corresponds to a square antiprism. Intermolecular interactions N…H–O, C–H…O, and C–H…F leading to the formation of supramolecular chains are observed in crystals of the complex. The UV-irradiated complex exhibits green luminescence caused by transitions 5D4 → 7Fj (j = 2–6) characteristic of the Tb3+ ion. The main photophysical luminescence parameters are determined, and the scheme of energy transfer in the complex is proposed. The synthesized compound can be of interest as an independent luminophore or as the initial substance for the synthesis of heteroligand complexes by the substitution of ethanol molecules in the internal coordination sphere.
592-603
Rhenium Iodide Cluster Re3I9 as a Precursor in the Synthesis of [Re(CO)5I] and ((н-C4H9)4N)2[Re2Cl8]
Аннотация
The reduction of rhenium iodide cluster Re3I9 to [Re(CO)5I] (55% yield) was observed in the presence of concentrated HCl and HCOOH at 130°C. In a dimethylammonium chloride [(CH3)2NH2]Cl melt, the triangular cluster polymer Re3I9 is transformed into the dianionic binuclear cluster complex [Re2Cl8]2–, which was isolated as the tetrabutylammonium salt ((n-C4H9)4N)2[Re2Cl8] in 46% yield. The structure of the complex [Re(CO)5I] was confirmed by powder X-ray diffraction, energy dispersive spectroscopy, IR spectroscopy, and Raman spectroscopy. ((n-C4H9)4N)2[Re2Cl8] was identified using elemental analysis, energy dispersive spectroscopy, and IR and Raman spectroscopy. An acetonitrile solution of ((n-C4H9)4N)2[Re2Cl8] was characterized by the mass spectrum and characteristic UV-Vis spectrum.
604-612
Synthesis and X-ray Structures of Polymeric Calcium Carboxylates
Аннотация
The reactions of calcium hydroxide with pivalic, 1-naphthoic, and 2-furancarboxylic acids afford the corresponding polymeric calcium carboxylates. Depending on the crystallization conditions, calcium pivalate is isolated as two different coordination polymers: [Ca3(Piv)6(DMF)2]n · 0.635nC6H6 · 0.365nDMF (I) and [Ca(Рiv)(H2O)2.333(DMF)0.666]n · nРiv·0.333H2O (II). The synthesized calcium 1-naphthoate contains coordinated water molecules [Сa(Naph)2(H2O)2]n (III), and calcium furoate [Ca(Fur)2]n (IV) contains no ancillary ligands. The structures of compounds I–IV are determined by X-ray diffraction (XRD) (CIF files CCDC nos. 2342790–2342793, respectively). The structures of compounds I–III are characterized by the 1D polymeric structure, and compound IV is the 3D polymer.
613-626