Molecular Dyads and Triads Based on Phenothiazine and π‐Extended Tetrathiafulvalene Donors, Bis(terpyridine)ruthenium(II) Complexes, and Polyoxometalates

Abstract

Molecular dyads were prepared by the functionalization of organic electron‐donor units, that is, a phenothiazine (PTZ) moiety and a π‐extended tetrathiafulvalene (exTTF) moiety, with bis(terpyridine)RuII complexes. In addition, the complexes were equipped with a terminal alkyne group, which was used for the coupling with a Keggin‐type polyoxometalate (POM). In this regard, molecular triads were prepared, whereby the central RuII complex should act as a photosensitizer and the POM as an electron acceptor. Certain spectral changes were observed upon attachment of the donors and the POM framework to the RuII complexes. In particular, the emission of the RuII complex became significantly reduced with increasing donor strength, which suggested an intramolecular electron transfer by reductive emission quenching. The introduction of the POM framework revealed no further quenching of the emission and is tentatively ascribed to the minor influence of the electron acceptor on the excited states of the RuII complex.

Tetrathiafulvalene and π-extended tetrathiafulvalene pillar[5]arene conjugates: synthesis, electrochemistry and host–guest properties

“…In the particular case of 7 , additional peaks corresponding to the successive loss of [(CH 3 S) 2 C 3 S 2 )] fragments were also detected. This characteristic fragmentation pattern of exTTF derivative 39 further confirmed the structure of 7 as these fragments can only arise from a fully clicked compound. The 1 H and 13 C NMR spectra of 3a–b and 7 were also fully consistent with their D 5 -symmetrical structures.…”

A photoredox catalysed Heck reactionviahole transfer from a Ru(ii)-bis(terpyridine) complex to graphene oxide

“…Bis-terpyridine Ru complexes have a very short lifetime of their excited state [1][2][3][4] which makes them less appealing for photocatalytic applications compared to other organic and metal organic dyes. [5][6][7][8][9] Recently, Schubert and Dietzek were able to directly show a photoinduced charge-separation between a bisterpyridine Ru complex covalently attached to a polyoxometalate unit.…”

“…Furthermore, they can be used to build linear structures without the danger to obtain geometric or optical isomers. 2,11,12 Yet, just recently a homoleptic complex has been used to build a photocatalytic active MOF material for the reduction of carbon dioxide. 20 Homoleptic bis-terpyridine iron complexes have been used to link nanoparticles.…”

Towards Covalent Photosensitizer-Polyoxometalate Dyads-Bipyridyl-Functionalized Polyoxometalates and Their Transition Metal Complexes

“…This finding can be attributed to an improved charge separation and electron transfer between the subunits in the covalently bound materials. These issues have been analyzed by the groups of Odobel, Mayer, and Harriman [19], Hanan and Hasenknopf [20], as well as Schubert and Dietzek [21,22].…”