Mapping the Assembly of Metal-Organic Cages into Complex Coordination Networks


Yadav, Ashok, Gupta, Arvind K, Steiner, Alexander ORCID: 0000-0002-4315-6123 and Boomishankar, Ramamoorthy (2017) Mapping the Assembly of Metal-Organic Cages into Complex Coordination Networks. CHEMISTRY-A EUROPEAN JOURNAL, 23 (72). pp. 18296-18302.

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Abstract

Structural transformations of supramolecular assemblies play an important role in the synthesis of complex metal-organic materials. Nonetheless, often little is known of the assembly pathways that lead to the final product. This work describes the conversion of cubic metal-organic polyhedra to connected-cage networks of varying topologies. The neutral cubic cage assembly of formula {Pd<sub>3</sub> [PO(NiPr)<sub>3</sub> ]}<sub>8</sub> (PZDC)<sub>12</sub> has been synthesized from {Pd<sub>3</sub> [(NiPr)<sub>3</sub> PO](OAc)<sub>2</sub> (OH)}<sub>2</sub> ⋅2 (CH<sub>3</sub> )<sub>2</sub> SO and 2,5-pyrazenedicarboxilic acid (PZDC-2H). This 42-component self-assembly is the largest known among the neutral cages with Pd<sup>II</sup> ions. The cage contains twenty-four vacant carboxylate O-sites at the PZDC ligands that are available for further coordination. Post-assembly reactions of the cubic cage with Fe<sup>II</sup> and Zn<sup>II</sup> ions produced cage-connected networks of dia and qtz topologies, respectively. During these reactions, the discrete cubic cage transforms into a network of tetrahedral cages that are bridged by the 3D metal ions. The robustness of the [Pd<sub>3</sub> {[PO(NiPr)<sub>3</sub> }]<sup>3+</sup> molecular building units made it possible to map the post-assembly reactions in detail, which revealed a variety of intermediate 1D and 2D cage networks. Such step-by-step mapping of the transformation of discrete cages to cage-connected frameworks is unprecedented in the chemistry of coordination driven assemblies.

Item Type: Article
Uncontrolled Keywords: cage framework, inter-conversion, metal-organic polyhedra, topology
Depositing User: Symplectic Admin
Date Deposited: 27 Oct 2017 14:45
Last Modified: 13 Feb 2024 15:26
DOI: 10.1002/chem.201704585
Related URLs:
URI: https://livrepository.liverpool.ac.uk/id/eprint/3010972
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