DOI: 10.25442/hku.30976777.v1
title: Supporting data for “<b>Synthesis Of Self-Assembled Metal-Organic Cage Nanoparticles For Various Applications</b>"

description: <b>Dataset description</b>This dataset contains research data generated during the course of the PhD project described in the associated thesis. The dataset includes:Photographic records of laboratory notebooks in JPEG format, documenting experimental procedures, observations, and synthetic workflows;Chemical structures, reaction schemes, and experimental conditions provided in PDF, PNG, and CDXML formats;Representative processed NMR spectra (¹H, and related experiments) exported in PDF and PNG formats;Extracted low-resolution mass spectra from LC–MS measurements provided as image files;Selected transmission electron microscopy (TEM) images of nanoparticle samples;Tabulated and summarized experimental data related to catalysis and cage-formation studies.Raw instrument data generated in proprietary formats (e.g. Bruker NMR raw files or LC–MS vendor software files) are not included due to storage and access limitations of instrument-managed systems. The processed and curated data provided here are sufficient to support interpretation of results and verification of the conclusions presented in the thesis.<br><i>Abstract</i>Metal–organic cages (MOCs) represent a versatile class of discrete, self-assembled supramolecular architectures formed by the coordination bond of metal ions and organic ligands. Their well-defined structures combine molecular-level precision with nanoscale dimensions, showing a wide variety of applications including drug delivery, catalysis, and supramolecular gels.<sub> </sub>Among various MOC systems, M<sub>12</sub>L<sub>24</sub> cuboctahedral cages have emerged as a powerful platform due to their synthetic robustness, modular ligand design, well-defined cavities, and dimensions compatible with bulky supramolecular guests. However, the broader application of MOCs, particularly toward multifunctional materials, remains limited by synthetic challenges associated with precise and orthogonal functionalization of the cage framework. This thesis aims to address a central synthetic challenge in this field: the development of dual-activated ligands that enable independent and precise <i>exo</i>- and <i>endo</i>-functionalization within a single M<sub>12</sub>L<sub>24</sub> framework, facilitating rational exploration of solubilization, molecular recognition, catalytic confinement, and anisotropic ligand incorporation.This thesis is composed of five chapters. Chapter 1 introduces the fundamental principles of MOCs and surveys their applications, with a focused discussion on M<sub>12</sub>L<sub>24</sub> cages in photonics, drug delivery, and catalysis.<b> </b>Chapter 2 critically reviews ligand-level synthetic strategies that lead to functional MOCs and analyzes their limitations. Building upon this review, a ligand design is proposed that preserves metal-directing motifs while incorporating orthogonal reactive handles. The iterative design process, synthetic obstacles, and solutions are discussed in detail. Based on the foundation of synthetic methodology, Chapter 3 applies our designed MOC for the application of drug delivery. A polymer–drug–ligand conjugate has been synthesized to allow simultaneous functionalization at the cage exterior and interior. The resulting block-copolymer-modified MOC micelles (BCPMMs) act as core–shell nanocarriers, with the most pronounced cytotoxicity observed for the upgraded drug-loaded system (BCPMM 2.0). Incorporation of a photoresponsive unit enables spatiotemporal control over drug release, and preliminary evidence of photo-triggered multi-drug synergy is observed in BCPMM 2.1. Chapter 4 extends the dual-functionalization concept to catalysis through the encapsulation of Cu(I) [2]-catenanes within Pd<sub>12</sub>L<sub>24</sub> cages. This system demonstrates how mechanically interlocked catalysts can be sterically confined and organized in a cage environment, opening pathways toward alloy-like or cooperative catalytic behavior.<b> </b>Chapter 5 summarizes these research works and provides a perspective for future study of this field.Overall, this thesis establishes a general ligand-design framework for dual <i>exo</i>- and <i>endo</i>-functionalized M<sub>12</sub>L<sub>24</sub> cages and demonstrates its utility in both therapeutic delivery and confined catalysis, providing a foundation for future multifunctional supramolecular systems.<br>