Programmable Vertical Expansion of Bilayer 2D Supramolecular Frameworks via Molecular Pillar Engineering
Abstract
AbstractAchieving quantitative control over interlayer spacing in multilayer two‐dimensional (2D) supramolecular organic frameworks (SOFs) remains a fundamental challenge. Here, we report a molecular pillar engineering strategy enabling programmable vertical expansion of bilayer architectures. By designing elongated bipyridine pillars L2/L3 (3.0/4.4 nm) with hydrophilic side chains, we transform a Zn‐porphyrin/CB[8] monolayer SOF (ml‐2D‐SOF, 1.8 nm) into bilayers with precision‐tuned thicknesses: bl‐2D‐SOF‐2 (5.4 ± 0.2 nm) and bl‐2D‐SOF‐3 (6.7 ± 0.3 nm). Synchrotron small‐angle and wide‐angle X‐ray scattering (SAXS/WAXS), transmission electron microscopy (TEM) lattice imaging, and atomic force microscopy (AFM) confirm structural regularity with Ångstrom‐level accuracy in layer spacing. Crucially, we establish a linear correlation between pillar length and interlayer distance, while multivalency‐driven assembly ensures >93% bilayer selectivity. This work pioneers quantitative 3D engineering in 2D SOFs, opening avenues for tailored nanoconfined environments.
Article Details
Authors (9)
Ting Zhou
Shi‐Xing Lei
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China
Biao Lv
College of Chemistry Zhengzhou University 100 Kexue Street Zhengzhou 450001 China
Xing‐Yu Guo
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences 345 Lingling Lu Shanghai 200032 China
Xiao‐Mei Gong
College of Chemistry Zhengzhou University 100 Kexue Street Zhengzhou 450001 China
Qiao‐Yan Qi
State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences Shanghai 200032 China
Jia Tian
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences
Zhan‐Ting Li
State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences Shanghai P. R. China
Bo Yang