Exploring the Subcomponent Self-Assembly of Three-Dimensional Architectures from Transition Metals and Heteroditopic Ligands

Abstract

Exploring the Subcomponent Self-Assembly of Three-Dimensional Architectures from Transition Metals and Heteroditopic Ligands. A thesis submitted to the University of Manchester for the degree of Doctor of Philosophy in the Faculty of Science and Engineering. Subcomponent self-assembly has become an attractive design strategy for the formation of functional three-dimensional container molecules, many of which have been employed for a wide variety of applications. The subcomponent syntheses described in this thesis utilise heteroditopic ligands and a range of transition metal salts to prepare a series of novel metal-organic complexes. Chapter one presents an introduction into supramolecular chemistry and the relevant inorganic principles utilised within the area for the formation of functional architectures. The chapter provides a review of the literature surrounding subcomponent self-assembly with a variety of ligands, highlighting the site-specific binding of different metal ions, as well as the stabilisation of metals in different spinstates. Chapter two reports the synthesis of a trigonal bipyramidal complex formed from a heteroditopic ligand, where iron was bound within the construct as low-spin iron(II), high-spin iron(II) and high-spin iron(III). This complex was the first literature example of a fluoride-bridged mixedvalence iron star, with six fluoride ions being abstracted from the tetrafluoroborate counterions. Chapter three highlights a series of analogous iron(II) and silver(I) trigonal bipyramidal complexes with different anions bound within the central cavity. The complex was also formed with copper(I) in place of silver for potential catalytic applications. In Chapter four, anion-induced self-sorting phenomena were explored to facilitate the formation of a heteroleptic tetrahedral iron(II) cage. Control over the sorting within the system was obtained through the choice of anion in the starting metal salt, with iron(II) perchlorate supporting integrative self-sorting. Chapter five contains results relevant to the work described in the preceding chapters. This work highlights a number of polynuclear architectures formed from both hetero- and homoditopic ligands in the presence of transition metal ions. The experimental procedures and characterisation for each compound are given. Lauren L. K. Taylor September 2021

Date of Award	1 Aug 2022
Original language	English
Awarding Institution	The University of Manchester
Supervisor	Imogen Riddell (Supervisor) & David Mills (Supervisor)