Tetranuclear d-f Metallostars: Synthesis, Relaxometric, and Luminescent Properties

Abstract : A novel ditopic ligand DTPA-ph-phen, based on 1,10-phenanthroline and diethylenetriaminepentaacetic acid (DTPA) units, has been designed and fully characterized by (1)H, (13)C, and 2D-COSY NMR spectroscopy, IR and electrospray ionization mass spectrometry (ESI-MS) techniques. The DTPA core of the ligand specifically binds Ln(III) ions (Ln = Eu, Gd) resulting in formation of the [Ln{DTPA-ph-phen}(H(2)O)](-) complex. The photophysical properties of the Eu(III) compound have been investigated, and the complex shows characteristic red luminescence with an overall quantum yield of 2.2%. Reaction of [Gd{DTPA-ph-phen}(H(2)O)](-) with Ru(II) leads to further self-assembly into a heterobimetallic metallostar complex containing Gd(III) and Ru(II) in a 3:1 ratio. This tetranuclear [(Gd{DTPA-ph-phen})(3)(H(2)O)(3)Ru](-) complex (Gd(3)Ru), formed by the coordination of Ru(II) to the 1,10-phenanthroline unit, has been characterized by a range of experimental techniques and evaluated toward its feasibility as a potential bimodal optical/MRI agent. The Gd(3)Ru metallostar shows intense metal-to-ligand charge transfer (MLCT) transition resulting in intense light absorption in the visible spectral region. Upon irradiation into this MLCT band at 450 nm, the Gd(3)Ru complex exhibits red broad-band luminescence in the range of 550-800 nm centered at 610 nm with a quantum yield of 4.8%. Proton nuclear magnetic relaxation dispersion (NMRD) measurements indicate that the Gd(3)Ru complex exhibits an enhanced relaxivity value r(1) of 36.0 s(-1) mM(-1) per metallostar molecule at 20 MHz and 310 K. The ability of the complex to noncovalently bind to human serum albumin (HSA) was investigated, but no significant interaction was detected.
Document type :
Journal articles
Complete list of metadatas

https://hal.archives-ouvertes.fr/hal-02103224
Contributor : Laëtitia Legoupil <>
Submitted on : Thursday, April 18, 2019 - 10:58:30 AM
Last modification on : Friday, April 19, 2019 - 1:29:51 AM

Identifiers

Collections

Citation

Geert Dehaen, Svetlana Eliseeva, Peter Verwilst, Sophie Laurent, Luce Vander Elst, et al.. Tetranuclear d-f Metallostars: Synthesis, Relaxometric, and Luminescent Properties. Inorganic Chemistry, American Chemical Society, 2012, 51 (16), pp.8775-8783. ⟨10.1021/ic300537y⟩. ⟨hal-02103224⟩

Share

Metrics

Record views

6