Giant Seebeck Effect of Dibenzo[ g,p ]chrysene and its Derivatives: Deuteration and Substituent Effects and Relationship with Interlayer Distance

Abstract Thermoelectric properties of undoped crystals of dibenzo[ g,p ]chrysene (DBC), deuterated DBC (DBC‐ d 16 ), and 2,10‐dimethyl‐DBC (DBC‐Me 2 ) have been studied to obtain some insights into the relationship between the structural parameters of materials and the giant Seebeck effect. X‐ray crystallography showed one‐dimensional columnar packing with the interlayer distances ( d ) for DBC‐ d 16 , DBC, and DBC‐Me 2 were 3.78 Å, 3.79 Å, and 3.91 Å, respectively. All three compounds formed one‐dimensional carrier transport pathways as suggested by the transfer integral calculations. Their Seebeck coefficients (α) were negative, indicating n‐type behavior. DBC‐ d 16 exhibited among the highest peak Seebeck coefficient (α max =−114 mV/K) compared to DBC and DBC‐Me 2 (α max =−31 and −22 mV/K, respectively). The power factors of DBC‐ d 16 and DBC‐Me 2 were higher than that of DBC, due to an increase in Seebeck coefficient and conductivity, respectively. Notably, a positive correlation was found between the peak temperature of the Seebeck coefficient and interlayer distance d , while |α max | correlated negatively with d . Deuteration significantly enhanced |α max |, likely due to reduced molecular vibrations, though further investigation should consider the effect of dynamic structural fluctuation caused by thermal motion.