An octahedral coordination cage with six Fe(<scp>iii</scp>) centers as a <i>T</i><sub>1</sub> MRI probe

Dissanayake, Aruni; Spernyak, Joseph A.; Morrow, Janet R.

doi:10.1039/d4cc03681f

Chem. Commun.

2024

DOI: 10.1039/d4cc03681f

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An octahedral coordination cage with six Fe(iii) centers as a T₁ MRI probe

Aruni Dissanayake,

Joseph A. Spernyak,

Janet R. Morrow

Abstract: The incorporation of multiple Fe(III) centers bridged by rigid ligands into a coordination cage represents a powerful approach for designing effective MRI contrast agents. In this context, an octahedral Fe(III)...

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2024

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Zn(II)-Responsive MRI Probe Based on an Fe(III) Macrocyclic Complex

Cineus,

Dissanayake,

Morrow

2024

Inorg. Chem.

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The development of responsive MRI contrast agents to detect fluctuations in Zn(II) is a growing area of research.Here we describe a high-spin Fe(III) coordination complex, Fe(ADAPT), as one of the first examples of an Fe(III) MRI probe that is responsive to Zn(II). The six-coordinate Fe(ADAPT) contains a phenolate-appended 1,4,7-triazacyclononane (TACN) ligand framework, with the phenolate groups linked to a Zn(II) binding moiety. Fe(ADAPT) lacks an exchangeable inner-sphere water and thus relies on second-and outer-sphere water interactions for proton relaxation. Fe(ADAPT) is highly kinetically inert under physiological conditions at pH 7.4 and 37 °C and to excess Zn(II) over 72 h. In the presence of 2 equiv of Zn(II) with a 200 μM Fe(III) probe, an increase in relaxivity of ∼80% is observed. A ternary complex among Fe(ADAPT), Zn(II), and human serum albumin leads to a nearly 200% increase in relaxivity.

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Zn(II)-Responsive MRI Probe Based on an Fe(III) Macrocyclic Complex

Cineus,

Dissanayake,

Morrow

2024

Inorg. Chem.

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Self-Assembled Tetrahedral [Cr^III₄L₆]¹²⁺ Cage Displaying Near-Infrared Spin-Flip Photoluminescence

Ye,

Cruz,

Doistau

et al. 2024

Inorg. Chem.

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The thermodynamically controlled self-assembly of bis-bidentate quaterpyridine ligand, L = 2,2′:5′,5″:2″,2‴-quaterpyridine, with Cr II and subsequent oxidation to Cr III yields the first photoluminescent tetrahedral [Cr III 4 L 6 ] 12+ molecular cage. Singlecrystal X-ray diffraction reveals the presence of two homochiral cages (ΛΛΛΛ and ΔΔΔΔ) in the unit cell that crystallize as a racemic mixture. Additionally, a PF 6 anion is observed inside the cavity, in line with isostructural cages built with Ni II or Fe II . Each corner of the polyhedron is occupied by weakly antiferromagnetically coupled {Cr(bipy) 3 } 3+ (bipy = 2,2′-bipyridine) patterns, as revealed by magnetometry. Upon light excitation in the UV−vis region, spin-flip luminescence from the 2 E/ 2 T 1 excited states with a maximum at 727 nm (13755 cm −1 ) was detected at room temperature. The measured excited state lifetime of 183 μs is longer than the 102 μs recorded for the mononuclear [Cr(bipy) 3 ] 3+ complex under anaerobic conditions, whereas the luminescence quantum yields are in the same order of magnitude and amount to 10 −2 %. The photoluminescence brightness, B, calculated using the maxima of the absorption spectra for both species, goes from 14 M −1 •cm −1 for the mononuclear compound to 90 M −1 •cm −1 for the tetrahedral cage. This 6-fold improvement is observed across the entire excitation wavelength range, and it is due to the incorporation of four light-harvester units in the molecular cage.

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An octahedral coordination cage with six Fe(iii) centers as a T₁ MRI probe

Abstract: The incorporation of multiple Fe(III) centers bridged by rigid ligands into a coordination cage represents a powerful approach for designing effective MRI contrast agents. In this context, an octahedral Fe(III)...

Cited by 2 publications

References 28 publications

Zn(II)-Responsive MRI Probe Based on an Fe(III) Macrocyclic Complex

Zn(II)-Responsive MRI Probe Based on an Fe(III) Macrocyclic Complex

Self-Assembled Tetrahedral [Cr^III₄L₆]¹²⁺ Cage Displaying Near-Infrared Spin-Flip Photoluminescence

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An octahedral coordination cage with six Fe(iii) centers as a T1 MRI probe

Abstract: The incorporation of multiple Fe(III) centers bridged by rigid ligands into a coordination cage represents a powerful approach for designing effective MRI contrast agents. In this context, an octahedral Fe(III)...

Cited by 2 publications

References 28 publications

Zn(II)-Responsive MRI Probe Based on an Fe(III) Macrocyclic Complex

Zn(II)-Responsive MRI Probe Based on an Fe(III) Macrocyclic Complex

Self-Assembled Tetrahedral [CrIII4L6]12+ Cage Displaying Near-Infrared Spin-Flip Photoluminescence

Contact Info

Product

Resources

About

An octahedral coordination cage with six Fe(iii) centers as a T₁ MRI probe

Self-Assembled Tetrahedral [Cr^III₄L₆]¹²⁺ Cage Displaying Near-Infrared Spin-Flip Photoluminescence