In this report,we theoretically designed a series of monometallic rhenium(I)tricarbonyl complexes containing [Re(CO)3]+fragment with pyca-2,6-iPr2C6H3–based ligand,which derived from its prototype complex 1(R=-H(1))by the introduction of different electron donating or withdrawing substituted groups(R=-NO2(2);-CHO(3);-OCH3(4);-NH2(5))on R position of N^N ligand.To obtain detailed insight into the electronic structures and spectroscopic properties of fac-[ReCl(CO)3(R-N^N)],we used the density functional theory(DFT)and time-dependent DFT(TD-DFT)computational methods.