Tetratopic and hexatopic terpyridine ligands as building blocks in coordination polymers

Manfroni, Giacomo. Tetratopic and hexatopic terpyridine ligands as building blocks in coordination polymers. 2023, Doctoral Thesis, University of Basel, Faculty of Science.


Official URL: https://edoc.unibas.ch/93846/

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The work described in this thesis concerns the synthesis of tetratopic bis(3,2':6',3''-tpy) and
bis(4,2':6',4''-tpy), hexatopic tris(3,2':6',3''-tpy) and tris(4,2':6',4''-tpy) ligands and their capability to
form 1D, 2D and 3D coordination polymers. The ligands were reacted with [Cu(hfacac)2]∙H2O,
[Zn(hfacac)2]∙2H2O and Co(NCS)2 under single-crystal growth conditions and the resulting crystals were
analysed by X-ray diffraction analysis. Good solubility in common organic solvents of the resulting
terpyridine building blocks was crucial for the successful crystallisation of the final assemblies. A variety
of solubilising substituents have been used throughout this thesis.
Chapter 1 introduces the discipline of coordination polymers. After a few definitions and an overview
of classic synthetic approaches to these materials, there follows an important section dealing with the
topological description of coordination networks. This is accompanied by an overview of the typically
used metal centres and polytopic ligands as building blocks for the assembly of coordination polymers,
followed by a focus on the terpyridine compounds. Finally, the chapter concludes with some selected
examples of applications to illustrate to the reader the great potential that this class of materials
Chapter 2 deals with the synthesis and coordination chemistry of V-shaped bis(3,2':6',3''-tpy) and
bis(4,2':6',4''-tpy) ligands. In previous works of Newkome and coworkers, analogous V-shaped
2,2':6',2''-isomers have been shown to be valuable precursors for the synthesis of even highly
sophisticated molecular constructs. However, the V-shaped bis(3,2':6',3''-tpy) and bis(4,2':6',4''-tpy)
ligands used in this thesis, did not prove to be effective for the synthesis of coordination polymers,
specifically the growth of single-crystals suitable for X-ray characterisation.
In Chapter 3, a combination of tetratopic bis(3,2':6',3''-tpy) ligands and [M(hfacac)2]∙xH2O (M = Cu, x =
1; M = Zn, x = 2) led to a series of 2D coordination polymers propagating in two dimensions. These
networks all share the same underlying (4,4) topology regardless of the nature of the solubilising
substituent, crystallisation solvent and configuration of the metal centres.
Chapter 4 describes the reaction of tetratopic bis(3,2':6',3''-tpy) ligands with a 4-connecting metal
centre, Co(NCS)2. Layering setups using MeOH and chlorobenzene led to the formation of 3D
assemblies with a cds topology. In contrast, a solvent switch from chlorobenzene to CHCl3 results in a
topological change to a 3D trinodal self-penetrating network. A comparison is then made with the most
recent findings obtained by a former Master's candidate in the Constable-Housecroft research group.
An extension beyond the usual 2-4 connecting terpyridine ligands is made in Chapter 5. Several
hexatopic tris(3,2':6',3''-terpyridine) and tris(4,2':6',4''-terpyridine) compounds were prepared and
reacted with [Cu(hfacac)2]∙H2O. The 3,2':6',3''- and 4,2':6',4''-isomers possess different coordination
flexibilities yielding an unexpected 1D coordination polymer and a predictable 2D network,
respectively. The former is the first single-crystal X-ray characterisation of a tris(terpyridine)-based
coordination polymer.
The general results of this thesis, with a brief outlook on the projects, are given in Chapter 6.
Advisors:Constable, Edwin Charles and Sparr, Christof and Fromm, Katharina
Faculties and Departments:05 Faculty of Science > Departement Chemie > Former Organization Units Chemistry > Anorganische Chemie (Constable)
UniBasel Contributors:Manfroni, Giacomo and Constable, Edwin Charles and Sparr, Christof
Item Type:Thesis
Thesis Subtype:Doctoral Thesis
Thesis no:14964
Thesis status:Complete
Number of Pages:vii, 121
Identification Number:
  • urn: urn:nbn:ch:bel-bau-diss149645
edoc DOI:
Last Modified:11 Mar 2023 05:30
Deposited On:10 Mar 2023 15:27

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