Enantiopure Polyradical Tetrahedral Pd12L6 Cages |
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Authors: | Dr Prabhakaran Rajasekar Abinash Swain Prof Dr Gopalan Rajaraman Prof Dr Ramamoorthy Boomishankar |
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Institution: | 1. Department of Chemistry, Indian Institute of Science Education and Research Pune, Pune, 411008 India;2. Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai, 400076 India |
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Abstract: | 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. |
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Keywords: | cages chirality palladium P−N ligands radicals |
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