Heteroatom incorporation at different positions of the molecule backbone is highly effective in tuning the molecular structures and optoelectronic properties of conjugated organic molecules. Here, to perform structure property relationship of the molecules on the optoelectronic device performance, the geometric structures of notr, cation and anion state, bond length alternation values (BLA), reorganization energy, frontier orbitals, iyonization potential and electronic affinity of (2E,6E)-2,6-bis(3-chlorobenzylidene)cyclohexanone molecule and its three derivatives were examined by using 3D single crystal geometri through theoretical calculations. Moreover, to further understand the optoelectronic device performance of the compounds, the π⋯π stacking types which are T, herringbone and antiparallel H type for the studied molecules were determined because device performance strongly depends on the molecular geometry and packing arrangements created with intermolecular π⋯π stacking and noncovalent interactions. According to our combination of experimental and theoretical studies, heteroatom substitution of the molecule backbone was revealed to lower both the hole and electron injection barriers. In addition, nonsubstituted molecule is electron transport material (ETM) while its three derivatives are hole‐transport materials (HTM) with the low electron and hole reorganization energies, respectively. The lower reorganization energy for hole and electrons of the molecules revealed that these molecules might be good charge transport contenders in optoelectronic device and provide a new focus of the molecular design of p and n type bishalcone organic electronic materials. The other theoretical results of this study and π⋯π stacking type of the molecules exactly support this result.
Anahtar Kelimeler: Marcus Electron Theory, Density Functionality Theory, Reorganization Energy, π⋯π Stacking Interactions, Charge Transfer Property, Optoelectronic Device.