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Copper(II) Perfluorinated Carboxylate Complexes with Small Aliphatic Amines as Universal Precursors for Nanomaterial Fabrication.

ABSTRACT: Copper(II) carboxylate compounds with ethylamine and isopropylamine of the general formula [Cu₂(RNH₂)₂(µ-O₂CR_f)₄], where R = Et, ⁱPr, and R_f = C_nF_2n+1, n = 1-6, were characterised in the condensed and gas phases by electron impact mass spectrometry (EI MS), IR spectroscopy, and thermal analysis. A mass spectra analysis confirmed the presence of metallated species in the gas phase. Among the observed fragments, the pseudomolecular ions [Cu₂(RNH₂)₂(µ-O₂CR_f)₃]⁺ were found, which suggests the dimeric structure of the studied complexes with axially N-coordinated ethyl- or isopropylamine molecules and bridging perfluorinated carboxylates. TGA studies demonstrated that copper transfer to the gas phase occurs even under atmospheric pressure. The temperature range of the [Cu₂(RNH₂)₂(µ-O₂CR_f)₄] and other copper carriers detection, observed in variable temperature infrared spectra, depends on the type of amine. The possible mechanisms of the decomposition of the tested compounds are proposed. The copper films were produced without additional reducing agents despite using Cu(II) CVD precursors in the chemical vapor deposition experiments. The layers of the gel-like complexes were fabricated in both spin- and dip-coating experiments, resulting in copper or copper oxide materials when heated. Dinuclear copper(II) carboxylate complexes with ethyl- and isopropylamine [Cu₂(RNH₂)₂(µ-O₂CR_f)₄] can be applied for the formation of metal or metal oxide materials, also in the nanoscale, by vapour and 'wet' deposition methods.

SUBMITTER: Szymanska IB

PROVIDER: S-EPMC8659220 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Given the huge significance of organic solvents in several industrial processes, the use of membranes for recovering the solvents has evolved into an industrially viable process. The current work has been focused on studying the effect of minor changes in the chemistry of the reacting monomers on the organic solvent nanofiltration/solvent resistance nanofiltration (OSN/SRNF) performance of the membranes. The two aliphatic amines with varying aliphatic chain lengths between primary and secondary amines were selected for this purpose. Based on the structure of the resultant active layer, the Janus nanofiltration performance of the membrane was evaluated. The two membranes, 4A-TPC@crosslinked PAN and 4A-3P@crosslinked PAN were fabricated by using two different tetra-amines, 4A (N,N'-bis(3-aminopropyl)ethylenediamine) and 4A-3P (N,N'-Bis(2-aminoethyl)-1,3-propanediamine) crosslinked with terephthaloyl chloride (TPC) on a crosslinked polyacryonitrile (PAN) support through interfacial polymerization (IP). The presence of multiple hydrophobic -CH2- groups in the structures of the aliphatic amines 4A and 4A-3P develops hydrophobic sites in the hydrophilic polyamide active layers of the membranes. In addition, 4A has two secondary amino groups separated by ethylene (-CH2-CH2-) groups, whereas in 4A-3P, the two secondary amino groups are separated by propylene (-CH2-CH2-CH2-) leading to variation in the structural features and performance of the two membranes. Both membranes were fully characterized by several membrane characterization techniques and applied for OSN/SRNF using both polar (methanol, ethanol, and isopropanol) and non-polar (n-hexane and toluene) solvents. Different dyes (Congo red, Eriochrome black T, and Methylene blue) were used as model solutes during the filtration experiment. The 4A-3P-TPC@crosslinked PAN showed n-hexane and toluene flux of 109.9 LMH and 95.5 LMH, respectively. The Congo red (CR) showed the highest rejection, reaching 99.1% for the 4A-TPC@Crosslinked PAN membrane and 98.8% for the 4A-3P-TPC@Crosslinked PAN membrane.

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Copper(II) Perfluorinated Carboxylate Complexes with Small Aliphatic Amines as Universal Precursors for Nanomaterial Fabrication.

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