Longfei Nan^#, Pei He^#, Tingwei Zhang, Yiran Dong, Chao Feng, Tong He, Pengfei Li, Yanfeng Zhang*, Yong Nie*, and Jiao Jiao*. J. Am. Chem. Soc. 2025, 147, 24430–24441. DOI: 10.1021/jacs.5c03381

Carboranes, distinguished by their three-dimensional aromaticity, electron-delocalized frameworks, and exceptional thermal/chemical stability, have emerged as versatile platforms in coordination chemistry, catalysis, functional materials, and optoelectronics. In luminescent systems, their dual functionality as steric spacers and electron-deficient units enables effective suppression of aggregation-caused quenching and modulation of charge-transfer dynamics in donor-acceptor architectures, thereby enhancing solid-state photoluminescence.

Despite extensive research on the luminescent properties of carborane derivatives in recent years, the development of chiral carborane-based luminescent compounds and exploration of their chiroptical properties remains a challenge constrained by synthetic limitations. Conventional strategies for CPL-active carboranes rely on either ① chiral alkyne-decaborane(14) addition or ② asymmetric B−H bond activation. These methods necessitate either toxic precursors (decaborane)/resource-intensive catalytic systems, or laborious enantiomer separation via HPLC, resulting in low scalability, high environmental footprint, and inadequate material throughput for comprehensive optoelectronic studies. Therefore, developing concise and eco-friendly asymmetric synthesis methods to achieve scalable and diverse access to optically pure carborane compounds is crucial for studying the properties and structure-activity relationships.

Herein, we developed a highly stereoselective and straightforward asymmetric synthesis for chiral carborane molecules. This method employs readily available starting materials and enables the precise construction of optically pure chirality-contiguous bridged carborane derivatives via a two-step, one-pot protocol, achieving scalable synthesis on a 10 gram-scale without chiral HPLC resolution. it has been observed that the introduction of carborane into the chiral bridging structure significantly enhances the Φ_PL and g_lum of the luminescent compounds. Such concurrent enhancement of both parameters is scarcely documented. Applying one of the chiral emissive compounds, a good enantioselective discrimination of several free amino acids in aqueous phase has been achieved.

First Authors: Nan Longfei, doctoral candidate, Dr. He Pei, Xi'an Jiaotong University

Correspondence Authors: Prof. Zhang Yanfeng, A/Prof. Jiao Jiao, Xi'an Jiaotong University; Prof. Nie Yong, University of Jinan

Full Text Link: https://pubs.acs.org/doi/10.1021/jacs.5c03381