期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 -, 期 -, 页码 -出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202301963
关键词
copper; dication diradicals; ferromagnetic spin coupling; heterodimers; nickel; porphyrins; structure elucidation
We report an unexpected rearrangement that leads to the formation of stable dinickel/dicopper chlorin-porphyrin dication diradical heterodimers. The bridge in these diradicals undergoes a nucleophilic attack at the beta-carbon of the porphyrin pi-cation radical, initiating the rearrangement process.
We report an unexpected rearrangement, controlled by the nature of the bridge, leading to the formation of novel, remarkably stable triply fused dinickel(II)/dicopper(II) chlorin-porphyrin dication diradical heterodimers in excellent yields. Here, a dipyrromethene bridge gets completely fused between two porphyrin macrocycles with two new C-C and one C-N bonds. The two macrocycles exhibit extensive pi-conjugation through the bridge, which results in an antiferromagnetic coupling between the two pi-cation radicals. In addition, the macrocyclic distortion also favours a rare intramolecular ferromagnetic interaction between the Cu-II and pi-cation radical spins to form a triplet state. The structural and electronic perturbation in the unconjugated dication diradical possibly enables the bridging pyrrolic nitrogen to undergo a nucleophilic attack at the nearby beta-carbon of the porphyrin pi-cation radical with a computed free energy barrier of >20 kcal mol(-1) which was supplied in the form of reflux condition to initiate such a rearrangement process. UV-vis, EPR and ESI-MS spectroscopies were used to monitor the rearrangement process in situ in order to identify the key reactive intermediates leading to such an unusual transformation.
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