Transformation of molecular compounds with Ba(Sr)/Al/Si and Ca(Sr, Ba)/Ti(Zr, Hf)/Si heteroelements as new efficient route to metal silicate materials

Petrus, Rafał; Drág-Jarzábek, Anna; Utko, Józef; Lis, Tadeusz; Sobota, Piotr

doi:10.1039/c8dt03796e

Cited by 4 publications

(4 citation statements)

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“…The chlorine anion Cl1 links four Ba II ions, forming a pyramid Ba 4 Cl cluster, in which the four Ba II ions occupy the vertices of the bottom square and the Cl1 is 0.799 Å away from the center of the bottom which Ba 4 Cl structure is only found in a Ba/Zr metal silicate cluster (Figure 1b). 13 The linkages of the four types of formate are distinct. The first formate anion (F1) adopts an anti-anti mode coordinating to Mn2 K and Mn2 using O1 and O2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The coordinated environment of Ba1 ions is very complicated, surrounded by one chlorine atom and seven oxygen atoms from six independent formate anions. The chlorine anion Cl1 links four Ba II ions, forming a pyramid Ba 4 Cl cluster, in which the four Ba II ions occupy the vertices of the bottom square and the Cl1 is 0.799 Å away from the center of the bottom which Ba 4 Cl structure is only found in a Ba/Zr metal silicate cluster (Figure b) …”

Section: Resultsmentioning

confidence: 99%

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[Ba₄Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba₄Cl][M₃(HCO₂)₁₃]}_n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

Zhang

et al. 2022

Inorg. Chem.

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Novel 3D metal formate frameworks {[Ba4Cl][M3(HCO2)13]} n (M = Mn for 1, Co for 2, and Mg for 3) were successfully assembled via microwave-assisted synthesis. The complexes are rare coordination polymers crystallized at space group P4cc with the polar point group C 4v . In the structure, the MII ions are bridged by two types of anti-anti formate in forming a 3D pcu framework, and additional formates coordinate to the unsaturated sites of the MII ions in the framework, giving an anionic M–formate net. Ba4Cl clusters take the cavities of the net as charge balance, in which the chloride ion deviates from the center of the barium ions. The asymmetric Ba4Cl structure is transmitted throughout the crystal resulting in polar structure, which is further confirmed by nonlinear optical and piezoelectric test. Nonlinear optical activity tests of 1 and 3 show SHG signals 0.32 and 0.28 times that of KDP, while 2 has a piezoelectric coefficient d 33 of 6.8 pC/N along polar axis. Magnetic studies reveal antiferromagnetic coupling between MII ions in 1 and 2. Spin canting was found only in 2 with anisotropic CoII ions, and 2 is a canted antiferromagnetically with T N = 5 K. Further field-induced spin flop was also found in 2 with a critical field 0.9 T.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

[Ba₄Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba₄Cl][M₃(HCO₂)₁₃]}_n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

Zhang

et al. 2022

Inorg. Chem.

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“…e ., 6) and thus suggest significant hydrolysis of the Si/Al core structure in combination with base-induced desilication. Direct thermal activation of Si–Ph bonds in other Si/Al-based MPs has been reported as an alternative method to synthesize amorphous silica–alumina matrixes and a type of crystalline feldspar. , Regardless, the transcription of the MP core structure into aluminosilicates remains challenging in general.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Microporous Aluminosilicate by Direct Thermal Activation of Phenyl-Substituted Single-Source Aluminosilicate Molecular Precursors

et al. 2022

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The construction of aluminosilicates from versatile molecular precursors (MPs) represents a promising alternative strategy to conventional processes based on monomeric molecular or polymeric Al and Si sources. However, the use of MPs often suffers from drawbacks such as the decomposition of the core structures in the presence of solvents, acids, or bases. In this work, we demonstrate a simple thermal synthesis of porous aluminosilicates from single-source spiro-7-type MPs that consist of a tetrahedral Al atom and six Si atoms functionalized with 12 phenyl (Ph) groups, (C + )[Al{Ph 2 Si(OSiPh 2 O) 2 } 2 ] − (C + [AlSi 6 ] − ; C + = pyridinium cation (PyH + ), Na + , K + , Rb + , or Cs + ), without using a solvent or activator. Microporous aluminosilicates synthesized via the thermal treatment of C + [AlSi 6 ] − under a 79% N 2 + 21% O 2 atmosphere exhibited extremely low carbon contents (0.10−1.28%), together with Si/Al ratios of 3.9−6.7 ± 0.2 and surface areas of 103.1−246.3 m 2 /g. The solid-state 27 Al and 29 Si MAS NMR spectra suggest that the obtained aluminosilicates with alkali cations retain a tetrahedral Al site derived from the spiro-7-type core structure. After a proton-exchange reaction, the aluminosilicates showed almost 1.5 times higher reactivity in the catalytic ring-opening of styrene oxide than the aluminosilicate before proton exchange due to the catalytically active OH site being predominantly bridged by tetrahedral Al and Si atoms. These results suggest that the present MP strategy is a promising method for the introduction of key structures into active inorganic materials.

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“…On the other hand, due to the absence of an energetically accessible vacant d π manifold, they can be used to synthesize homo- and heterometallic coordination entities [ 2 , 3 ], leading to, among others, efficient catalysts [ 4 ] and molecular precursors for solid-state metal silicate-based materials [ 5 ]. Such molecular precursors guarantee dispersion of metal sources at the molecular level and provide uniform reaction sites for conversion to the ceramic.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structures, and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities

et al. 2021

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In alkali metal and lanthanide coordination chemistry, triphenylsiloxides seem to be unduly underappreciated ligands. This is as surprising as that such substituents play a crucial role, among others, in stabilizing rare oxidation states of lanthanide ions, taking a part of intramolecular and molecular interactions stabilizing metal-oxygen cores and many others. This paper reports the synthesis and characterization of new lithium [Li4(OSiPh3)4(THF)2] (1), and sodium [Na4(OSiPh3)4] (2) species, which were later used in obtaining novel gadolinium [Gd(OSiPh3)3(THF)3]·THF (3), and erbium [Er(OSiPh3)3(THF)3]·THF (4) triphenylsiloxides. Crystal structures were determined for all 1–4 compounds, and in addition, IR, Raman, absorption spectroscopy studies were conducted for 3 and 4 lanthanide compounds. Furthermore, direct current (dc) variable-temperature magnetic susceptibility measurements on polycrystalline samples of 3 and 4 were carried out in the temperature range 1.8–300 K. The 3 shows behavior characteristics for the paramagnetism of the Gd3+ ion. In contrast, the magnetic properties of 4 are dominated by the crystal field effect on the Er3+ ion, masking the magnetic interaction between magnetic centers of neighboring molecules.

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Transformation of molecular compounds with Ba(Sr)/Al/Si and Ca(Sr, Ba)/Ti(Zr, Hf)/Si heteroelements as new efficient route to metal silicate materials

Abstract: The heterometallic alkoxides based on M–O–M′–O–Si motif were used for the preparation of ceramic materials consisting of mixed metal oxide nanocrystallites embedded in SiO2 matrix.

Cited by 4 publications

References 37 publications

[Ba₄Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba₄Cl][M₃(HCO₂)₁₃]}_n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

[Ba₄Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba₄Cl][M₃(HCO₂)₁₃]}_n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

Synthesis of Microporous Aluminosilicate by Direct Thermal Activation of Phenyl-Substituted Single-Source Aluminosilicate Molecular Precursors

Synthesis, Crystal Structures, and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities

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Transformation of molecular compounds with Ba(Sr)/Al/Si and Ca(Sr, Ba)/Ti(Zr, Hf)/Si heteroelements as new efficient route to metal silicate materials

Abstract: The heterometallic alkoxides based on M–O–M′–O–Si motif were used for the preparation of ceramic materials consisting of mixed metal oxide nanocrystallites embedded in SiO2 matrix.

Cited by 4 publications

References 37 publications

[Ba4Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba4Cl][M3(HCO2)13]}n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

[Ba4Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba4Cl][M3(HCO2)13]}n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

Synthesis of Microporous Aluminosilicate by Direct Thermal Activation of Phenyl-Substituted Single-Source Aluminosilicate Molecular Precursors

Synthesis, Crystal Structures, and Spectroscopic Properties of Novel Gadolinium and Erbium Triphenylsiloxide Coordination Entities

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[Ba₄Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba₄Cl][M₃(HCO₂)₁₃]}_n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties

[Ba₄Cl] Cations Directed Perovskite-like Polar Metal Formate Frameworks {[Ba₄Cl][M₃(HCO₂)₁₃]}_n (M = Mn, Co, and Mg): Microwave-Assisted Synthesis, Structures, and Properties