The Ru(II) and BF2; complexes of calixsmaragdyrin were prepared under simple reaction conditions and characterized by HR-MS, 1D and 2D NMR spectroscopy, optical spectroscopy, and electrochemistry, and the structure of the Ru(II) complex of calixsmaragdyrin was elucidated by Xray crystallography. The crystal structure of the Ru(II) complex revealed that the Ru(II) ion is hexacoordinate withthe three pyrrole-nitrogen ligands-,i from the tripyrrin unit of the calixsmaragdyrin macrocycle, and the remaining coordination sites of Ria(II) ion were occupied by two carbonyl groups and one hydroxyl (-OH) group. The calixsmaragdyrin macrocycle in the complex was distorted with a dome -like structure. In the BF2 complex of calixsmaragdyrin, the BF2 unit was bound to two pyrrolic nitrogens of the dipyrrin moiety of calixsntaragdyrin as deduced by detailed 1- and 2-dimensional NMR spectroscopy studies. The complex displayed a strong Soret-like absorption band at 449 rim with the absence of Qbands, Whereas, the BEJ, complex showed a Soret-like band at 475 nm with two weldefined Qbands at 787 and 883 run, respectively: Quantum mechanical DFT calculations yielded relaxed equilibrium structures that were similar to the X-ray crystal structures, and the-related charge density distributions indicated that the d orbital of the Ru(II) fop, was contributing to the HOMO and LUMG states. In addition,-TD-DFT calculations successfully reproduced the large bathochromic shifts, oscillator strengths, and electronic transitions that were observed in-the experimental absorption spectra of all three complexes. Both the Ru(II) and the BF2 complexes of calcsmatagdyrin were stable under redox conditions.