Monitoring Mn2+ coordination with [Re4Q4(CN)12]4- clusters by NMR relaxation: Chalcogen effects on coordination polymer-based nanoarchitecture formation and MRI performance

Monitoring Mn2+ coordination with [Re4Q4(CN)12]4- clusters by NMR relaxation: Chalcogen effects on coordination polymer-based nanoarchitecture formation and MRI performance Full article

Journal

Journal of Magnetism and Magnetic Materials
ISSN: 0304-8853 , E-ISSN: 1873-4766

Output data

Year: 2026, Volume: 656, Article number : 174450, Pages count : 9 DOI: 10.1016/j.jmmm.2026.174458

Tags

NMR relaxation Rhenium cluster Coordination polymer formation Protein crown Mn-based contrast agent

Authors

Akhmadeev B.S. ^1,2 , Gavriliak M.S. ³ , Parfenova K.A. ³ , Nizameeva G.R. ² , Kholin K.V. ⁴ , Voloshina A.D. ¹ , Gerasimova T.P. ¹ , Gubaidullin A.T. ¹ , Pronin A.S. ⁵ , Mironov Yu.V. ⁵ , Mustafina A.R. ¹

Affiliations

1	A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov str., 420088 Kazan, Russian Federation
2	Kazan National Research Technological University, K. Marx Str. 68, 420015 Kazan, Russian Federation
3	Kazan (Volga Region) Federal University, Kremlyovskaya str., 18, 420008, Kazan, the Russian Federation
4	Department of Nanotechnology in Electronics, Kazan National Research Technical University named after A.N. Tupolev-KAI, 10 Karl Marx Str, Kazan, Russia 420111
5	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Ave, 630090 Novosibirsk, Russian Federation

Funding (1)

This work presents a rare example of monitoring the coordination of Mn2+ aqua ions with [Re4Q4(CN)12]4 (Q = S2 , Se2 , Te2 ) clusters, leading to the formation of coordination polymer nanoarchitectures in aqueous solutions, using nuclear magnetic relaxation and dynamic light scattering methods. X-ray powder diffraction analysis allows us to estimate the exact stoichiometry of Mn2[Re4Q4(CN)12] (Q = Se2 , Te2 ) nanocrystallites measuring 20 nm, while amorphous Mnx[Re4S4(CN)12] nanoparticles are 10 nm. The nature of the chalcogen atom in the cluster core critically affects the efficiency and kinetics of nanoarchitecture formation. The coordination of the sulfide cluster with Mn2+ immediately triggers the formation of amorphous nanoparticles, while the selenide and telluride analogs exhibit a less thermodynamically favorable coordination, which, nevertheless, facilitates the formation of crystalline nanoparticles. Mn2[Re4Se4(CN)12] nanoparticles, due to their lower aggregation compared to Mn2[Re4Te4(CN)12] and less dense packing within the aggregates compared to Mnx[Re4S4(CN)12] provide an optimal basis for high magnetic relaxivity with r1(2) values, reaching 20 and 40 mM- 1 s- 1 in solutions simulating blood serum. Thus, both the high r1(2) values of nanocrystallites self-generated in aqueous solutions of Mn2+ and [Re4Se4(CN)12]4- clusters and their low cyto- and hemotoxicity highlight the potential of these nanoparticles for further development of manganese-based contrast agents for magnetic resonance imaging (MRI).

Akhmadeev B.S. , Gavriliak M.S. , Parfenova K.A. , Nizameeva G.R. , Kholin K.V. , Voloshina A.D. , Gerasimova T.P. , Gubaidullin A.T. , Pronin A.S. , Mironov Y.V. , Mustafina A.R.
Monitoring Mn2+ coordination with [Re4Q4(CN)12]4- clusters by NMR relaxation: Chalcogen effects on coordination polymer-based nanoarchitecture formation and MRI performance
Journal of Magnetism and Magnetic Materials. 2026. V.656. 174450 :1-9. DOI: 10.1016/j.jmmm.2026.174458 WOS Scopus OpenAlex

Submitted:	May 19, 2026
Accepted:	Jul 29, 2026
Published online:	Aug 6, 2026
Published print:	Oct 15, 2026

≡ Web of science:	WOS:001847371300001
≡ Scopus:	2-s2.0-105046721329
≡ OpenAlex:	W7196952543