Ligands Derived from Tetrathiafulvalene: Building Blocks for Multifunctional Materials

Abstract

The last decade has witnessed many advances in the coordination chemistry of tetrathiafulvalene (TTF). Various ligands, in which a metal-binding functionality is attached to the TTF unit, have been synthesized and used for the preparation of metal complexes. This Perspective summarizes the main types of TTF-containing ligands and their metal complexes and outlines the potential for the use of these building blocks in the design and assembly of multifunctional molecular materials.

Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(ii) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties

“…15 The observed Pt-C and CuC are identical on the two TTF fragments (Table 1). These CuC bond lengths are longer than that found in the Me 3 TTFCuCH precursor (1.152(8) Å) 8 but lie in the same range as that found in trans-RuCl-(-CuCMe 3 TTF)(dppe) 2 (1.203(3) Å). 6 The angle between the two alkynes in 1 amounts to 88.92(20)°.…”

“…This cathodic shift reveals that the organometallic fragment, through the acetylide linker, increases the electron density on the TTF cores and thus highlights the electronic interaction between the platinum center and the TTF cores. Such a cathodic shift has only been previously observed in a few cases such as for (Me 2 TTF(SiMe 2 ) 2 )Pt-(PPh 3 ) 2 , 26 trans-ClRu(CuCMe 3 TTF)(dppe) 2 6 and trans-Ru (CuCMe 3 TTF) 2 (dppe) 2 . 8 It is worth noting that this shift depends on the metal linked to the TTF acetylide ligand.…”

“…[1][2][3][4][5] To study these interactions between the TTF moiety and the metal center, another approach has been recently developed which relies on organometallic chemistry and on the connection of a TTF to the metal center through a conjugated carbon chain. To date only four examples of such hybrid organic-inorganic building blocks have been reported, and all of them involve one or two TTF acetylide ligands coordinated to a metal center (Chart 1).…”

Syntheses, characterization and properties of rhenium(I) tricarbonyl complexes based on tetrathiafulvalene substituted naphthyridine ligands

“…Owing to the typical π donor ability and attractive redox properties of tetrathiafulvalene (TTF), the synthesis and coordination chemistry of versatile ligands containing TTF core have attracted great interest during last decades [1][2][3][4][5]. A variety of heteroatom-based ligands, which are famous for their coordination ability to transition metal ions, including pyridine [6][7][8] and bipyridine [9][10][11][12], acetylacetonate [13][14][15], dithiolate [16,17], phosphine [18][19][20][21], carboxyl [22][23][24], are linked to the TTF core by covalent linkages.…”

Effective tuning of the electronic and photophysical properties of tetrathiafulvalene pyrroles via aromatic heterocycle annulation

“…3 This research has gone beyond the initial emphasis on electrically conducting materials and now encompasses various fields, such as functional material chemistry, nonlinear optics, photovoltaics, molecular electronics, redox active molecular receptors, molecular switches, logic gates, and artificial machines to name but a few. [3][4][5][6][7][8] Among the various fields of research related to the synthetic chemistry of TTF and its analogues, we are particularly interested in the preparation and study of new functional TTF building blocks bearing fused heterocyclic aromatic rings, especially pyrroles. Pyrroles are versatile synthetic building blocks in organic synthesis and have proved to be very important intermediates in the construction of a wide range of natural products 9 and functional supramolecular architectures.…”