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3 protocols using tetramethylorthosilicate

1

Synthesis and Characterization of Silica-based Materials

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PdCl2 (Silversalt, St. Petersburg, Russia, 98%), LiCl (TTX, Sergiev Posad, Russia, 98+), isopropanol (IPA, 99.5+%, Acros, Fair Lawn, NJ, USA), tetramethylorthosilicate (TMOS, Acros, 99%), (3-aminopropyl)trimethoxysilane (APTMS, Acros, 95%), N-(2-aminoethyl)-3-(trimethoxysilyl)propylamine (AEAPTMS, Sigma-Aldrich, St. Louis, MO, USA, 97%), (S)-(+)-2-phenylglycine methyl ester hydrochloride (Acros, 97%), L-phenylalanine methyl ester hydrochloride (Acros, 98%), methanol (Acros, 99.9%), hexene-1 (Acros, 97%), benzene (Sigma-Aldrich, 99.8%), acetophenone (Acros, 98%), benzaldehyde (Acros, 98+%), benzophenone (Acros, 99%), hexyne-1 (Acros, 98%), dicyclopentadiene (Merck, Darmstadt, Germany, 98%), cyclohexanone (Acros, 99.8%) and 1,4–dioxane (Acros, 99+%) were used without further purification. Lithium tetrachloropalladate (II) was prepared by mixing 1 mol of PdCl2 and 2 mol of LiCl in methanol and stirring for 24 h at room temperature.
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2

Synthesis of Functionalized Silica Materials

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Tetramethyl orthosilicate
(TMOS, 99%), dry Ethanol (99.5%, extradry, absolute), and dry toluene
(99.85%, extradry over a molecular sieve) were purchased from Acros
Organics. Poly(ethylene glycol) (PEG, Mn = 10 000) was purchased from Fluka. Ethanol (99.8%) was purchased
from Fisher Chemicals. Urea (≥99.5%) and (3-aminopropyl)trimethoxysilane
(APTMS, 97%) were purchased from Sigma-Aldrich. Acetic acid (100%)
was purchased from Carl Roth. MEthanol (≥99.85%) was purchased
from Chemsolute. Benzaldehyde (purified by redistillation, ≥99.5%),
ethyl cyanoacetate (≥98%), p-chloroBenzaldehyde
(97%), p-tolualdehyde (97%), and biphenyl-4-carboxaldehyde
(99%) were purchased from Aldrich. p-Anisaldehyde
was purchased from TCI. PEEK tubes (1/4 in. outer diameter ×
3.17 mm inner diameter, 50 cm length) were purchased from BGB Analytik.
PTFE shrink tubes (shrink rate 4:1) were purchased from AUTEC GmbH.
All chemicals were used without further purification.
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3

Synthesis of Yttrium-Zirconium-Silicate Compounds

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Yttrium nitrate hexahydrate (99%) and acetylacetone (AcAc, 99.5%) were purchased from Sigma-Aldrich Inc. (St. Louis, MO, USA); zirconium propoxide (ZIP, 70% sol. in 1-propanol), lithium methoxide (LiOMe, 2.2M sol. in methanol), and tetramethyl orthosilicate (TMOS 99%) were purchased from Acros Organics (Acros Organics™, Thermo Fisher Scientific, Waltham, MA, USA). All reagents were used as received. Methanol, ethanol, and isopropanol were kept on 3A molecular sieves for 48 h and further distilled under dry nitrogen.
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