Increased Antiaromaticity through Pentalene Connection in [n]Cyclo-1,5-dibenzopentalenes

Conjugated nanohoops incorporating nonalternant hydrocarbons have altered optoelectronic properties compared to [n]­cycloparaphenylenes or other purely aromatic hoops. We synthesized [n]­cyclo-1,5-dibenzopentalenes (n = 4, 5), in which nonalternant dibenzo­[a,e]­pentalenes are connected through their pentalene units. This leads to an increase in antiaromatic character and low-lying LUMO energies. Calculations show puckered or entangled conformations of the precursor macrocyclic Pt-complexes. Our study proves dibenzopentalene as a versatile nonalternant building block for conjugated nanohoops with modifiable antiaromaticity and optoelectronic properties.