Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and
DFT-Calculated 27Al NMR Parameters

J 2024

Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters

KEJÍK, Martin, Jiri BRUS, Lukas JEREMIAS, Lucie ŠIMONÍKOVÁ, Zdeněk MORAVEC et. al.

Basic information

Original name

Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters

Authors

KEJÍK, Martin (203 Czech Republic, belonging to the institution), Jiri BRUS, Lukas JEREMIAS, Lucie ŠIMONÍKOVÁ (203 Czech Republic, belonging to the institution), Zdeněk MORAVEC (203 Czech Republic, belonging to the institution), Libor KOBERA, Aleš STÝSKALÍK (203 Czech Republic, belonging to the institution), Craig E. BARNES and Jiří PINKAS (203 Czech Republic, guarantor, belonging to the institution)

Edition

Inorganic Chemistry, American Chemical Society, 2024, 0020-1669

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 4.600 in 2022

Organization unit

Faculty of Science

DOI

http://dx.doi.org/10.1021/acs.inorgchem.3c04035

UT WoS

001158206500001

Keywords in English

Aromatic compounds; Condensation; Ligands; Materials; Nuclear magnetic resonance spectroscopy

Abstract

V originále

Porous aluminosilicates are functional materials of paramount importance as Lewis acid catalysts in the synthetic industry, yet the participating aluminum species remain poorly studied. Herein, a series of model aluminosilicate networks containing [L–AlO3] (L = THF, Et3N, pyridine, triethylphosphine oxide (TEPO)) and [AlO4]− centers were prepared through nonhydrolytic sol–gel condensation reactions of the spherosilicate building block (Me3Sn)8Si8O20 with L–AlX3 (X = Cl, Me, Et) and [Me4N] [AlCl4] compounds in THF or toluene. The substoichiometric dosage of the Al precursors ensured complete condensation and uniform incorporation, with the bulky spherosilicate forcing a separation between neighboring aluminum centers. The materials were characterized by 1H, 13C, 27Al, 29Si, and 31P MAS NMR and FTIR spectroscopies, ICP-OES, gravimetry, and N2 adsorption porosimetry. The resulting aluminum centers were resolved by 27Al TQ/MAS NMR techniques and assigned based on their spectroscopic parameters obtained by peak fitting (δiso, CQ, η) and their correspondence to the values calculated on model structures by DFT methods. A clear correlation between the decrease in the symmetry of the Al centers and the increase of the observed CQ was established with values spanning from 4.4 MHz for distorted [AlO4]− to 15.1 MHz for [THF–AlO3]. Products containing exclusively [TEPO–AlO3] or [AlO4]− centers could be obtained (single-site materials). For L = THF, Et3N, and pyridine, the [AlO4]− centers were formed together with the expected [L–AlO3] species, and a viable mechanism for the unexpected emergence of [AlO4]− was proposed.

Links

EH22_008/0004572, research and development project

Name: Kvantové materiály pro aplikace v udržitelných technologiích

GJ20-03636Y, research and development project

Name: Nové katalyzátory pro přípravu 1,3-butadienu z ethanolu

Investor: Czech Science Foundation

LM2023042, research and development project

Name: Česká infrastruktura pro integrativní strukturní biologii

Investor: Ministry of Education, Youth and Sports of the CR, CIISB - Czech Infrastructure for Integrative Structural Biology

90254, large research infrastructures

Name: e-INFRA CZ II

Citovat

KEJÍK, Martin, Jiri BRUS, Lukas JEREMIAS, Lucie ŠIMONÍKOVÁ, Zdeněk MORAVEC, Libor KOBERA, Aleš STÝSKALÍK, Craig E. BARNES and Jiří PINKAS. Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters. Inorganic Chemistry. American Chemical Society, 2024, vol. 63, No 5, p. 2679-2694. ISSN 0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.3c04035.

@article{2371497,
   author = {Kejík, Martin and Brus, Jiri and Jeremias, Lukas and Šimoníková, Lucie and Moravec, Zdeněk and Kobera, Libor and Stýskalík, Aleš and Barnes, Craig E. and Pinkas, Jiří},
   article_number = {5},
   doi = {http://dx.doi.org/10.1021/acs.inorgchem.3c04035},
   keywords = {Aromatic compounds; Condensation; Ligands; Materials; Nuclear magnetic resonance spectroscopy},
   language = {eng},
   issn = {0020-1669},
   journal = {Inorganic Chemistry},
   title = {Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters},
   url = {https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04035},
   volume = {63},
   year = {2024}
}

TY  - JOUR
ID  - 2371497
AU  - Kejík, Martin - Brus, Jiri - Jeremias, Lukas - Šimoníková, Lucie - Moravec, Zdeněk - Kobera, Libor - Stýskalík, Aleš - Barnes, Craig E. - Pinkas, Jiří
PY  - 2024
TI  - Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters
JF  - Inorganic Chemistry
VL  - 63
IS  - 5
SP  - 2679-2694
EP  - 2679-2694
PB  - American Chemical Society
SN  - 00201669
KW  - Aromatic compounds
KW  - Condensation
KW  - Ligands
KW  - Materials
KW  - Nuclear magnetic resonance spectroscopy
UR  - https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c04035
N2  - Porous aluminosilicates are functional materials of paramount importance as Lewis acid catalysts in the synthetic industry, yet the participating aluminum species remain poorly studied. Herein, a series of model aluminosilicate networks containing [L–AlO3] (L = THF, Et3N, pyridine, triethylphosphine oxide (TEPO)) and [AlO4]− centers were prepared through nonhydrolytic sol–gel condensation reactions of the spherosilicate building block (Me3Sn)8Si8O20 with L–AlX3 (X = Cl, Me, Et) and [Me4N] [AlCl4] compounds in THF or toluene. The substoichiometric dosage of the Al precursors ensured complete condensation and uniform incorporation, with the bulky spherosilicate forcing a separation between neighboring aluminum centers. The materials were characterized by 1H, 13C, 27Al, 29Si, and 31P MAS NMR and FTIR spectroscopies, ICP-OES, gravimetry, and N2 adsorption porosimetry. The resulting aluminum centers were resolved by 27Al TQ/MAS NMR techniques and assigned based on their spectroscopic parameters obtained by peak fitting (δiso, CQ, η) and their correspondence to the values calculated on model structures by DFT methods. A clear correlation between the decrease in the symmetry of the Al centers and the increase of the observed CQ was established with values spanning from 4.4 MHz for distorted [AlO4]− to 15.1 MHz for [THF–AlO3]. Products containing exclusively [TEPO–AlO3] or [AlO4]− centers could be obtained (single-site materials). For L = THF, Et3N, and pyridine, the [AlO4]− centers were formed together with the expected [L–AlO3] species, and a viable mechanism for the unexpected emergence of [AlO4]− was proposed.
ER  -

KEJÍK, Martin, Jiri BRUS, Lukas JEREMIAS, Lucie ŠIMONÍKOVÁ, Zdeněk MORAVEC, Libor KOBERA, Aleš STÝSKALÍK, Craig E. BARNES and Jiří PINKAS. Lewis Acidic Aluminosilicates: Synthesis, 27Al MQ/MAS NMR, and DFT-Calculated 27Al NMR Parameters. \textit{Inorganic Chemistry}. American Chemical Society, 2024, vol.~63, No~5, p.~2679-2694. ISSN~0020-1669. Available from: https://dx.doi.org/10.1021/acs.inorgchem.3c04035.

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