[5]Cumulene Bridged Tri(9-anthryl)methyl Dimer

Towards the synthesis and evaluation of stable radical-based 2D frameworks, a diacetylene-bridged tri(9-anthryl)methyl (TAntM) radical dimer was designed and synthesized. X-ray crystallographic analysis revealed a strong spin-spin interaction between TAntM radical units through the diacetylene linker, resulting in a closed-shell [5]cumulene structure as the stable form. Variable-temperature (VT) 1H-NMR measurements at high temperatures showed signal broadening for aromatic protons, indicating an increased population of thermally excited triplet species as a metastable form. To facilitate spin-state modulation by external stimuli, mechanical grinding in the solid state was conducted. Due to its reactivity, mechanical grinding partially induced structural changes to radical species in the solid state.