Intercalates of Vanadyl Phosphate with Unsaturated Alcohols

Abstract

Intercalates of VOPO4 with several linear unsaturated alcohols (2‐propen‐1‐ol, 2‐buten‐1‐ol, 2‐propyn‐1‐ol, 2‐butyn‐1‐ol, 3‐butyn‐1‐ol 2‐pentyn‐1‐ol, 3‐pentyn‐1‐ol, 4‐pentyn‐1‐ol, 5‐hexyn‐1‐ol, 2‐octyn‐1‐ol, and 10‐undecyn‐1‐ol) have been prepared and characterized by powder X‐ray diffractometry, IR and Raman spectrometry, and thermogravimetry. The arrangement of the alcohol molecules with respect to the type and position of the multiple bonds in the carbon chain is proposed. Alcohols with terminal triple bonds form very stable intercalates. It is presumed that these alcohols are anchored to the host layers by donor‐acceptor bonds between their oxygen atoms and the vanadium atoms of the host, and by H‐bonding between the acetylenic hydrogen of the terminal carbon and the oxygen atoms of the host.

Intercalates of Vanadyl Phosphate with Branched Alcohols

“…The rest of the alcohol molecules should be bonded by hydrogen bonds only and placed in the cavities among the donor‐acceptor‐bonded molecules. A similar principle of the guest arrangement was proposed for the intercalate of vanadyl phosphate with propargyl alcohol 17…”

Synthesis and Characterization of Vanadyl Phosphate Intercalated with Dioxane, Trioxane, and 18-Crown-6

“…The position of the VO stretching vibration at 993 cm -1 in the Raman spectrum (observed at 1004 and 995 cm -1 for the 5-hexyn-1-ol and THP intercalates, respectively) 17,32 indicates a coordination of O guest to the vanadium atom of the host. This band is observed as a shoulder at about 998 cm -1 (1007, 1002, and 995 cm -1 for 5-hexyn-1-ol, acetone, , and THP 32 intercalates, respectively) in the infrared spectrum, allowing us to distinguish this band from other bands belonging to the intercalated dioxane molecules. The vanadyl stretching band appears to be especially sensitive to the atoms coordinated to vanadium within an octahedral arrangement in the host lattice structure.…”

“…Vanadyl phosphate forms a number of intercalation compounds with molecular guests having Lewis base character . Intercalations of aliphatic and aromatic amines, − carboxylic acids and their derivatives, amino acids, metallocenes, , alcohols, − diols, ,, ketones, , aldehydes, and poly(ethylene) glycols were studied. Great attention was devoted to the intercalation of heterocyclic N- and S-donors.…”

Novel Vanadium(V) Compounds with a Layer Structure: Synthesis, Crystal Structures, and Solid State NMR Spectroscopy of [(VO2)2(4,4‘-bpy)0.5(4,4‘-Hbpy)(XO4)]·H2O (X = P and As)

“…Intercalations of amines, heterocycles, carboxylic acids, amino acids, metallocenes, alcohols, aldehydes, and poly-(oxyethylene) compounds have been studied. [16][17][18] These intercalation reactions permit controlled systematic changes in the electronic properties of the host lattice, and they are of practical use as sensors. To promote specific chemical reactions or to enhance particular physical properties, new types of host materials are often required.…”

“…It readily undergoes redox intercalation reactions with alkali-metal and alkaline-earth-metal cations in the presence of a proper reducing agent. , It also forms a large number of intercalation compounds with a variety of molecular guests having Lewis base character. Intercalations of amines, heterocycles, carboxylic acids, amino acids, metallocenes, alcohols, aldehydes, and poly(oxyethylene) compounds have been studied. − These intercalation reactions permit controlled systematic changes in the electronic properties of the host lattice, and they are of practical use as sensors. To promote specific chemical reactions or to enhance particular physical properties, new types of host materials are often required.…”