期刊
NEW JOURNAL OF CHEMISTRY
卷 46, 期 15, 页码 6899-6920出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d2nj00296e
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资金
- Slovenian Research Agency [P1-0134]
- MICINN [PID2019-110856GA-I00]
- CNRS
- University of Bordeaux
- Region Nouvelle Aquitaine and Quantum Matter Bordeaux
The reactions between [Cu(quin)(2)(H2O)] and a series of aliphatic amino alcohols resulted in structurally diverse copper(II) complexes with different ligands and coordination modes.
The reactions between [Cu(quin)(2)(H2O)] (quin(-) = the anionic form of quinoline-2-carboxylic acid) and a series of aliphatic amino alcohols have yielded structurally very diverse copper(II) complexes, labelled a-g. Single-crystal X-ray structure analysis has revealed either intact amino alcohol molecules or amino alcoholate ions serving as ligands. In type a complexes, the amino alcohols are bound in a monodentate manner via NH2. Engagement of both functional groups in coordination was observed for types b and e (a bidentate chelating mode) and type c (a bidentate bridging one) complexes. In view of the strong bidentate chelating coordination of quinaldinate in [Cu(quin)(2)(H2O)], the formation of homoleptic amino alcohol complexes e was not anticipated. Equally surprising was the transformation of a mononuclear starting material into a one-dimensional (1D) coordination polymer, [Cu(quin)(2)](n) (g). Spontaneous deprotonation of some amino alcohols and coordination of, thus formed, amino alcoholates via both donors also took place. Dinuclear complexes (d) contained two bridging amino alcoholates, whilst bidentate chelating mode was observed for type f. Interestingly, the dinuclear complex exists as two isomers which differ in the position of quinaldinates with respect to the Cu(mu-OR)(2)Cu core. DFT calculations on isolated syn- and anti-[Cu-2(quin)(2)(3a1pO)(2)] (3a1pO(-) = anion of 3-amino-1-propanol) have shown the syn isomer to be more stable. The explanation lies in the intramolecular pi center dot center dot center dot pi stacking of quinaldinates, possible only in this isomer. Magnetic susceptibility measurements revealed antiferromagnetic interactions between S = 1/2 copper(II) spins in all the studied compounds except in [Cu(quin)(2)](n) (g) for which weak ferromagnetic couplings are detected.
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