Abstract A new series of disk-like cyclobutadienecobalt derivatives symmetrically substituted by lateral alkoxy groups with different chain lengths (− O (CH2) nCH3, n= 5, 6, 8, and 12) were prepared and their thermal phase transition behavior was studied in detail by optical measurements using crossed polarizers and differential scanning calorimetry (DSC). These cyclobutadienecobalt derivatives revealed dimorphism: two types of crystals K1 and K2 ( ...