Physical properties associated with charge transfer processes of tailored triphenylamine derivative molecules, generated from six nitrogen-containing heterocyclic aromatic cores (nTPAM), were theoretically studied. The conformer-rotamer ensemble sampling tool (CREST) was employed to study the geometric arrangements of n-TPAM monomers and dimers. Essential chemical parameters, such as reorganisation energies, spin densities, and chemical reactivity, were computed utilising the M06 and ωB97X-3c DFT functionals. The ω parameter of the ωB97X-3c functional was optimised through a non-empirical tuning method. Time-dependent DFT computations yielded insights into the maximum absorption wavelength and transition density matrix of n-TPAM monomers. The electronic coupling between dimers was assessed using M06 and ωB97X-3c. The HOMO energy levels of the n-TPAM derivatives correspond with the perovskite conduction band, situated between YZ22 and spiro-OMeTAD hole transport materials (HTMs). n-TPAM molecules demonstrated enhanced electronic coupling for hole transfer, except for C-TPAM (