International audienceSynthetic pathways to a range of potentially N3O-tetradentate ligands designed to coordinate to rhenium cores, as well as their coordination behaviors towards different rhenium cores (oxidation states +I and +V) are investigated. Two functionalized N-{[1-(4-R)-1H-1,2,3-triazol-4-yl]methyl}-2-(pyridin-2-ylmethoxy)aniline derivatives L1H (R = methyl acetate) and L2H (R = 4-nitrophenyl) act exclusively as bidentate ligands and lead to the formation of mononuclear tricarbonylrhenium(I) complexes of the general formula [(LH)Re(CO)3Cl] with L = L1 or L2. Both complexes are characterized by 1H NMR and 13C NMR, FTIR spectroscopy, electrospray ionization mass spectrometry, and in the case of [(L2H)Re(CO)3Cl], single-crystal X-ray diffraction. The rhenium is coordinated by three carbonyl groups, a chlorine atom and two nitrogen atoms of a triazole group, and a nitrogen of the aniline ring of the ligand, respectively. A theoretical study shows complex [(L2H)Re(CO)3Cl] is the most stable structural isomer. In addition, the oxorhenium(V) complex [(L3)ReO] is isolated and fully characterized after the reaction of the ReV precursor [ReOCl3(PPh3)2] with L3H3 [methyl 2-(4-{[2-(2-hydroxyphenylamino)-2-oxoethylamino]methyl}-1H-1,2,3-triazol-1-yl)acetate]. Its corresponding 99mTc complex was achieved with a good radiochemical yield (andgt; 90 %). The convenient synthesis of this ligand, coupled with its high affinity for [ReO]3+ and [99mTcO]3+ cores, make it a promising chelator for biomedical applications. © 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinhei