No abstract

The tri-tert-butylphenalenyl (TBPLY) radical exists as a π dimer in the crystal form with perfect overlapping of the singly occupied molecular orbitals (SOMOs) causing strong antiferromagnetic exchange interactions. 2,5-Di-tert-butyl-6-oxophenalenoxyl (6OPO) is a phenalenyl-based air-stable neutral π radical with extensive spin delocalization and is a counter analogue of phenalenyl in terms of the topological symmetry of the spin density distribution. X-ray crystal structure analyses showed that 8-tert-butyl- and 8-(p-XC6H4)-6OPOs (X=I, Br) also form π dimers in the crystalline state. The π-dimeric structure of 8-tert-butyl-6OPO is seemingly similar to that of TBPLY even though its SOMO-SOMO overlap is small compared with that of TBPLY. The 8-(p-XC6H4) derivatives form slipped stacking π dimers in which the SOMO-SOMO overlaps are greater than in 8-tert-butyl-6OPO, but still smaller than in TBPLY. The solid-state electronic spectra of the 6OPO derivatives show much weaker intradimer charge-transfer bands, and SQUID measurements for 8-(p-BrC6H4)-6OPO show a weak antiferromagnetic exchange interaction in the π dimer. These results demonstrate that the control of the spin distribution patterns of the phenalenyl skeleton switches the mode of exchange interaction within the phenalenyl-based π dimer. The formation of the relevant multicenter-two-electron bonds is discussed.

A new stable neutral radical with intramolecular hydrogen bonding, 2,5,8-tri-tert-butyl-7-hydroxy-6-oxophenalenoxyl, was synthesized from the corresponding dihydroxyphenalenone and isolated as a stable solid under air atmosphere at room temperature. The structure was unequivocally determined by means of IR spectra, ESR/ENDOR techniques, and DFT calculations.