@article{Li2026, 
author = {Wei Li and Haoyang Li and Yuxiao Zhang and Fanfei Meng and Jie Liu and Dongxu Cui and Xinlong Wang and Zhongmin Su and Chunyi Sun},
title = {Precise engineering of highly stable titanium-oxo clusters: From synergistic co-assembly to electrochemical detection},
year = {2026},
journal = {Nano Research},
volume = {19},
number = {3},
pages = {94908235},
keywords = {electrochemical sensors, titanium-oxo clusters, scorpionate ligands, synergistic co-assembly},
url = {https://www.sciopen.com/article/10.26599/NR.2025.94908235},
doi = {10.26599/NR.2025.94908235},
abstract = {Primitive reaction synergy is an effective strategy to construct complex assemblies, but the exploration is still in its infancy. Here, we report an organic–inorganic co-assembly method involving controlled dehydration condensation between boric acid and pyrazole which enables the precise synthesis of five titanium-oxo clusters (TOCs) with two distinct titanium-oxo cores. The parallelepiped Ti8O8 core which constructed from the mono-dehydration product (H2R1Bpz2O) with multiple μ3-O bridges exhibited enhanced structural stability and induced conformational distortion for open metal site exposure. Crucially, the tetrahedral Ti4O6 core which was capped with C3v-symmetric pyrazolylborate ligands (HR2Bpz3) via the first-reported in situ bis-dehydration exhibited unprecedented acid/base stability (pH tolerance: −0.778–15.079), surpassing all prior TOCs. Mechanistic studies, supported by stepwise balanced chemical equations, reveal water’s dual role in pyrazolylborate formation: mediating dehydration condensation and cluster nucleation, thus bridging organic–inorganic co-assembly. As a biosensor, 2,4-2FTi8@rGO/GCE electrode delivers benchmark electrochemical performance for chlorogenic acid (CGA), featuring ultrahigh sensitivity (9.486 μA·μM−1), nanomolar detection limit (6.59 nM) and a wide linear range (0.1–140 μM). It represents one of the few examples that simultaneously integrates all these key performance advantages. Theoretical calculations indicate that the stronger adsorption of 2,4-2FTi8 toward reaction species leads to its better electrochemical detection performance than MeBTi4. This work establishes a synthetic paradigm for TOCs via organic–inorganic co-assembly and highlights their electrochemical sensing potential.}
}