Premium
Enantiopure Polyradical Tetrahedral Pd 12 L 6 Cages
Author(s) -
Rajasekar Prabhakaran,
Swain Abinash,
Rajaraman Gopalan,
Boomishankar Ramamoorthy
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202101239
Subject(s) - diradical , enantiopure drug , electron paramagnetic resonance , crystallography , chemistry , magnetochemistry , paramagnetism , ferromagnetism , materials science , crystal structure , catalysis , nuclear magnetic resonance , condensed matter physics , organic chemistry , enantioselective synthesis , singlet state , atomic physics , physics , excited state
The synthesis of cages with a polyradical framework remains a challenging task. Herein is reported an enantiomeric pair of quinoid‐bridged polyradical tetrahedral palladium(II) cages that are stabilized by an unusual dianionic diradical form (dhbq ..2− ). These cages have been characterized by electron paramagnetic resonance and UV‐visible spectroscopy, squid magnetometry and mass spectrometry. Single‐crystal‐derived X‐ray investigations of the iso‐structural cages built on fluoranilate linkers confirm the tetrahedral structure of the obtained radical cages. Theoretical calculations showed that the diradical state of the dhbq anions is more stable than the usual monoradical state. A weak ferromagnetic exchange between adjacent radical centers was observed in DFT studies.