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- Title
Anion-Directed Metallocages: A Study on the Tendency of Anion Templation.
- Authors
Wu, Jing‐Yun; Zhong, Ming‐Shiou; Chiang, Ming‐Hsi
- Abstract
Self-assembly of Cu(NO3)2 ⋅3 H2O and di(3-pyridylmethyl)amine (dpma) with addition of different acids (HNO3, HOAc, HCl, HClO4, HOTf, HPF6, HBF4, and H2SO4) afforded a family of anion-templated tetragonal metallocages with a cationic prismatic structure of [(G n−)⊂{Cu2(Hdpma)4}](8− n)+ (G n−=NO3−, PF6−, SiF62−) with different ligating anions/solvents (NO3−, Cl−, ClO4−, OTf−, H2O) outside the cage. Systematic competitive experiments have rationalized the tendency of anion templation towards the formation of metallocages [(G n−)⊂{Cu2(Hdpma)4}](8− n)+ as occurring in the order SiF62−≈PF6−>NO3−>SO42−≈ClO4−≈BF4−. This sequence is mostly elucidated by shape control over size selectivity and electrostatic attraction between the cationic {Cu2(Hdpma)4}8+ host and the anionic guests. In addition, these results have also roughly ranked the anion coordination ability in the order Cl−, ClO4−, OTf−>NO3−>BF4−, CH3SO4−. Magnetic studies of metallocages 1 t and 2- 4 suggest that the fitted magnetic interaction, being weakly magnetically coupled overall, is interpreted as a result of the combination of intracage ferromagnetic coupling integrals and intercage antiferromagnetic exchange; both contributions are very weak and comparable in strength.
- Subjects
COPPER compounds; AMINES; ANIONS; COORDINATION compounds; METAL compounds
- Publication
Chemistry - A European Journal, 2017, Vol 23, Issue 63, p15957
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201702848