文献类型：期刊文献

英文题名：Programmable Higher-Order Topological Phases in Open-Shell Metal-Organic Frameworks

作者：Li, Can[1];Wang, Ying[2,3];Jiang, Yashi[1];Liu, Yufeng[1];Wu, Yi[2];Han, Yan-Jie[3];Chen, Zhen-Qiang[3];Liu, Liang[1,4];Liu, Xiaoxue[1,4];Guan, Dandan[1,4];Li, Yaoyi[1,4];Zheng, Hao[1,4];Liu, Canhua[1,4];Liu, Pei-Nian[2];Jia, Jinfeng[1,4];Li, Deng-Yuan[2];Wang, Shiyong[1,4]

机构：[1]Shanghai Jiao Tong Univ, Minist Educ, Key Lab Artificial Struct & Quantum Control, Tsung Dao Lee Inst,Sch Phys & Astron, Shanghai 200240, Peoples R China;[2]China Pharmaceut Univ, Sch Pharm, Key Lab Nat Med, Nanjing 211198, Peoples R China;[3]East China Univ Sci & Technol, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]Hefei Natl Lab, Hefei 230088, Peoples R China

年份：2025

卷号：147

期号：43

起止页码：39662

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20254419421349);WOS:【SCI-EXPANDED(收录号:WOS:001596579500001)】；

基金：We thank NSFC (Grants No. 22325203, No. 92365302, No. 92265105, 92065201, No. 12074247, No. 12174252, No. 22272050, No. 12304230, No. 22161160319), the National Key R&D Program of China (Grants No. 2024YFF0727100, Grants No. 2020YFA0309000), the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB28000000) and the Science and Technology Commission of Shanghai Municipality (Grants No. 2019SHZDZX01, No. 20QA1405100, No.24LZ1401000, No. 22QA1403000), Cultivation Project of Shanghai Research Center for Quantum Sciences (Grant No. LZPY2024-04), Innovation program for Quantum Science and Technology (Grant No. 2021ZD0302500), and Shanghai Jiao Tong University 2030 Initiative for financial support.

语种：英文

外文关键词：Chelation - Cobalt - Crystalline materials - Fractals - Ligands - Molecular orbitals - Molecules - Organometallics - Quantum theory - Scanning tunneling microscopy - Shells (structures) - Topology

摘要：Metal-organic frameworks (MOFs) offer remarkable structural and functional tunability across chemistry, physics and materials science, yet most MOFs built from closed-shell ligands remain wide-gap insulators, limiting their electronic functionality. Here we introduce a general strategy for imparting programmable topology to MOFs by leveraging open-shell ligands. Integrating radical nanographene linkers-featuring singly occupied molecular orbitals-into cobalt-coordination networks via on-surface synthesis, we create MOFs on Au(111) with emergent electronic states spanning the Fermi level. As a proof of concept, we synthesize Sierpinski-triangle fractal MOFs and directly observe topologically protected corner modes-the hallmarks of higher-order topological phases-using low-temperature scanning tunneling microscopy/spectroscopy. Through precise, molecule-by-molecule tip-induced assembly, we systematically tune the fractal hierarchy and monitor the evolution of topological states, supported by tight-binding simulations that align with experimental data. Our work establishes open-shell ligand chemistry as a versatile route to topological MOFs, paving the way for designer molecular quantum materials with programmable electronic and quantum properties.