Node‐Encoded Control of Lanthanide Self‐Assembly Enables Predictable and Water‐Stable Polyhedra for Bioimaging
- 1State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fuzhou China
- 2Department of Chemistry Jinan University Guangzhou China
- 3School of Pharmacy Gannan Medical University Ganzhou China
Abstract
Multinuclear lanthanide‐organic polyhedra offer attractive molecular scaffolds for biomedical imaging, while their predictable construction remains challenging because the high coordination numbers and kinetic lability of lanthanide ions often compromise both topological fidelity and aqueous stability. Here, we develop a coordination‐node‐encoding strategy in which a deprotonation‐stabilized terpyridine‐bis(tetrazolate) chelate preorganizes the local lanthanide coordination environment and thereby programs subsequent self‐assembly. Systematic variation of ligand connectivity affords a family of anionic lanthanide‐organic polyhedra spanning triangular, macrocyclic, tetrahedral, and trigonal‐prismatic topologies. Structural analyses and control experiments demonstrate that cooperative pentadentate chelation coupled with deprotonation imposes the directional coordination constraints required for topology‐selective assembly, while the anionic tetrazolate‐rich surfaces enhance the hydrophilic character and aqueous compatibility of the assemblies. The GdIII truncated‐tetrahedral polyhedron exhibits a per‐GdIII longitudinal relaxivity of 27.9 mM−1·s−1 at 9.4 T and 298 K, approximately sevenfold higher than that of Gd‐DTPA measured under identical conditions, corresponding to a molecular relaxivity of 167.1 mM−1·s−1. The EuIII analogues display characteristic red luminescence with high photoluminescence quantum yields (up to 54%) and enable low‐toxicity cellular imaging. Mixed Eu/Gd polyhedra further integrate EuIII luminescence and GdIII magnetic‐resonance contrast within a single molecular architecture, enabling luminescence and MR imaging. This work establishes coordination‐node encoding as a modular design principle for predictable lanthanide polyhedron formation and provides a versatile platform for developing multifunctional lanthanide‐based imaging systems with enhanced aqueous compatibility.
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BibTeX
@article{gan2026nodeencoded,
title = {{Node‐Encoded Control of Lanthanide Self‐Assembly Enables Predictable and Water‐Stable Polyhedra for Bioimaging}},
author = {Xin‐Ran Gan and Guanning Huang and Shao‐Jun Hu and Ze‐Hong Chen and Fan Yin and Li‐Peng Zhou and Xi Meng and Xiao‐Qing Guo and Tianfeng Chen and Qing‐Fu Sun},
journal = {Aggregate},
year = {2026},
month = oct,
doi = {10.1002/agt2.70469},
url = {https://doi.org/10.1002/agt2.70469},
note = {CC BY},
}
RIS
TY - JOUR
TI - Node‐Encoded Control of Lanthanide Self‐Assembly Enables Predictable and Water‐Stable Polyhedra for Bioimaging
AU - Xin‐Ran Gan
AU - Guanning Huang
AU - Shao‐Jun Hu
AU - Ze‐Hong Chen
AU - Fan Yin
AU - Li‐Peng Zhou
AU - Xi Meng
AU - Xiao‐Qing Guo
AU - Tianfeng Chen
AU - Qing‐Fu Sun
PY - 2026
DA - 2026/10/31
JO - Aggregate
DO - 10.1002/agt2.70469
UR - https://doi.org/10.1002/agt2.70469
AB - Multinuclear lanthanide‐organic polyhedra offer attractive molecular scaffolds for biomedical imaging, while their predictable construction remains challenging because the high coordination numbers and kinetic lability of lanthanide ions often compromise both topological fidelity and aqueous stability. Here, we develop a coordination‐node‐encoding strategy in which a deprotonation‐stabilized terpyridine‐bis(tetrazolate) chelate preorganizes the local lanthanide coordination environment and thereby programs subsequent self‐assembly. Systematic variation of ligand connectivity affords a family of anionic lanthanide‐organic polyhedra spanning triangular, macrocyclic, tetrahedral, and trigonal‐prismatic topologies. Structural analyses and control experiments demonstrate that cooperative pentadentate chelation coupled with deprotonation imposes the directional coordination constraints required for topology‐selective assembly, while the anionic tetrazolate‐rich surfaces enhance the hydrophilic character and aqueous compatibility of the assemblies. The GdIII truncated‐tetrahedral polyhedron exhibits a per‐GdIII longitudinal relaxivity of 27.9 mM−1·s−1 at 9.4 T and 298 K, approximately sevenfold higher than that of Gd‐DTPA measured under identical conditions, corresponding to a molecular relaxivity of 167.1 mM−1·s−1. The EuIII analogues display characteristic red luminescence with high photoluminescence quantum yields (up to 54%) and enable low‐toxicity cellular imaging. Mixed Eu/Gd polyhedra further integrate EuIII luminescence and GdIII magnetic‐resonance contrast within a single molecular architecture, enabling luminescence and MR imaging. This work establishes coordination‐node encoding as a modular design principle for predictable lanthanide polyhedron formation and provides a versatile platform for developing multifunctional lanthanide‐based imaging systems with enhanced aqueous compatibility.
SN - 2692-4560
ER -