A new metallostar complex based on an aluminum(iii) 8-hydroxyquinoline core as a potential bimodal contrast agent

Abstract

A ditopic DTPA monoamide derivative containing an 8-hydroxyquinoline moiety was synthesized and the corresponding gadolinium(III) complex ([Gd(H5)(H₂O)]⁻) was prepared. After adding aluminum(III), the 8-hydroxyquinoline part self-assembled into a heteropolymetallic triscomplex [(Gd5)₃Al(H₂O)₃]³⁻. The magnetic and optical properties of this metallostar compound were investigated in order to classify it as a potential in vitro bimodal contrast agent. The proton nuclear magnetic relaxation dispersion measurements indicated that the relaxivity r₁ of [Gd(H5)(H₂O)]⁻ and [(Gd5)₃Al(H₂O)₃]³⁻ at 20 MHz and 310 K equaled 6.17 s⁻¹ mM⁻¹ and 10.9 s⁻¹ mM⁻¹ per Gd(III) ion respectively. This corresponds to a relaxivity value of 32.7 s⁻¹ mM⁻¹ for the supramolecular complex containing three Gd(III) ions. The high relaxivity value is prominently caused by an increase of the rotational tumbling time τ_R by a factor of 2.7 and 5.5 respectively, in comparison with the commercially used MRI contrast agent Gd(III)–DTPA (Magnevist®). Furthermore, upon UV irradiation, [(Gd5)₃Al(H₂O)₃]³⁻ exposes green broad-band emission with a maximum at 543 nm. Regarding the high relaxivity and the photophysical properties of the [(Gd5)₃Al(H₂O)₃]³⁻ metallostar compound, it can be considered as a lead compound for in vitro bimodal applications.