Anion-Directed Metallocages: A Study on the Tendency of Anion Templation.
Chemistry
; 23(63): 15957-15965, 2017 Nov 13.
Article
in En
| MEDLINE
| ID: mdl-28895232
ABSTRACT
Self-assembly of Cu(NO3 )2 â
3 H2 O and di(3-pyridylmethyl)amine (dpma) with addition of different acids (HNO3 , HOAc, HCl, HClO4 , HOTf, HPF6 , HBF4 , and H2 SO4 ) afforded a family of anion-templated tetragonal metallocages with a cationic prismatic structure of [(Gn- )â{Cu2 (Hdpma)4 }](8-n)+ (Gn- =NO3- , PF6- , SiF62- ) with different ligating anions/solvents (NO3- , Cl- , ClO4- , OTf- , H2 O) outside the cage. Systematic competitive experiments have rationalized the tendency of anion templation towards the formation of metallocages [(Gn- )â{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- , CH3 SO4- . 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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Chemistry
Journal subject:
QUIMICA
Year:
2017
Document type:
Article
Affiliation country:
Taiwán