In the process of spent fuel reprocessing, it is highly difficult to extract transplutonium elements from adjacent actinides. A deep understanding of the electronic structure of transplutonium complexes is essential for development of steady ligands for in-group separation of transplutonium actinides. In this work, we have systematically explored the potential in-group separation ability of transplutonium elements of typical quadridentate N-donor ligands (phenanthroline-derived bis-triazine, BTPhen derivatives) through quasi-relativistic density functional theory (DFT). Our calculations demonstrate that ligands with electron-donating groups have stronger coordination abilities, and the substitutions of Br and phenol at the 4-position of the 1,10-phenanthroline have a higher effect on the ligand than those at the 5-position. Bonding analysis indicates that the covalent interaction of An3+ complexes becomes stronger from Am to Cf apart from Cm, which is because the energy of the 5f orbital gradually decreases and becomes energy-degenerate with the 2p orbitals of ligands. The most negative values of binding energies indicate the higher stability of Cf3+ complexes, in line with the larger covalency in the Cf-L bonds compared with An-L (An = Am, Cm, Bk). In addition, electron-donating group phenol can enhance the covalent interaction between ligands and heavy actinides. Consequently, the extraction ability of ligands with electron-donating substituents for heavy actinides is generally stronger than other ligands. Nevertheless, these ligands exhibit diverse separation abilities to in-group actinide recovery. Therefore, the enhancement of covalency does not necessarily lead to the improvement of separation ability, which may be caused by different extraction abilities. Compared with the tetradentate N, O-donor ligands (2,9-diamide-1,10-phenanthrolinel, DAPhen derivatives), species with BTPhen ligands display stronger covalent interaction and higher extraction capacity. In terms of in-group separation ability, the BTPhen ligands seem to have advantages in separation of californium from curium, while the DAPhen ligands possess stronger abilities to separate americium from curium. These results may afford some afflatus for the development of effective agents for in-group separation of transplutonium elements.