Design of Metal–Organic Assemblies via Shape Complementarity and Conformational Constraints in Dual Curvature Ligands
(2023) CCS Chemistry — Vol. 5, n° 11, p. 2506-2518 (2023)
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- 10 Biological building blocks AQ2 with low symmetry and flexibility, while common in biological systems, pose 11 numerous problems for synthetic self-assembly such 12 as the formation of isomers of assemblies that are 13 usually difficult to distinguish and purify. In this work, 14 three aromatic amide-based ligands (L1-L3) with a 15 central 1,8-diazatriptycene core were designed and 16 used for self-assembly with Pd 2+. While hundreds 17 of stereoisomers based on the conformational 18 flexibility around the amides and the unsymmetrical 19 nonplanar structure of the core are possible upon 20 coordination with the metal, the constraints 21 designed into the ligands direct the self-assembly 22 toward only a single Pd 2 L 4 cage (L1) or Pd 4 L 8 23 double-walled metallomacrocycle (L2) structure, 24 even in mixtures of the ligands. This structural ap-25 proach and the modularity of the ligand synthesis 26 affords ready access to deep cavitands with endohe-27 dral functionalization (L3). These results highlight 28 the potential of this new design strategy and open 29 the door to selectively functionalized cavity-based 30 architectures for numerous applications. 32 32 33 34 35 Introduction 36 Self-assembly and folding play essential roles in the 37 complexity and function of proteins. 1-3 In recent decades, 38 the possibility of generating synthetic molecules with 39 similar complexity and functions has inspired significant 40 progress in the design of self-assembled cavitands. 4-12 41 While numerous strategies for the self-assembly of such 42 structures have been developed, the combination of 43 organic ligands and metal ions for the formation of 44 metal-organic architectures has emerged as a highly 45 promising approach. 13-18 Notably, the combination of 46 Pd 2+ or Pt 2+ with ditopic ligands for the formation of 47 M n L 2n structures has attracted substantial attention and 48 led to some of the largest well-defined systems. 19-21 49 A wide range of applications related to their cavities has 50 been reported, including sensing, catalysis, drug delivery, 51 storage, and molecular recognition. 22-29 52 Unlike synthetic building blocks, the folding of pep-53 tides leads to subunits for self-assembly that have 54 not only complex electrostatic potential surfaces but also 55 a wide diversity of shapes. 30,31 The resulting high
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Liu, C.-L., Bobylev, E., Dauriac, S., Kauffmann, B., Reek, J., Robeyns, K., Garcia, Y., & Singleton, M. (2023). Design of Metal–Organic Assemblies via Shape Complementarity and Conformational Constraints in Dual Curvature Ligands. CCS Chemistry, 5(11), 2506-2518. https://doi.org/10.31635/ccschem.023.202302940 (Original work published 2023)