Multifunctional switching properties of “wire-like” dinuclear ruthenium bis-alkynyl spiropyran complexes

Abstract

Multifunctional switches are crucial to the development of smart molecular materials and molecular-electronic applications. Here, we describe the synthesis, structure, and characterization of several spiropyrans functionalized with alkynyl-[Ru(dppe)2] moieties. Through...

Multistate Switching of Some Ruthenium Alkynyl and Vinyl Spiropyran Complexes

“…This contrasts with the 31 P{ 1 H} NMR spectra of 16 and 17 , in which the diastereotopic nature of the phosphorus atoms results in an AB spin system ( J PP = 15 Hz). The stereocenter of the spiropyran ligand makes the phosphorus nuclei of the dppe ligand diastereotopic for complexes 16 – 19 . The fact that this peak manifests as an apparent singlet in the 31 P{ 1 H} NMR spectra for 16 and 17 is thought to be a result of coincidental equivalence of the chemical shifts in CD 2 Cl 2 .…”

“…We recently reported the synthesis of some ethynylspiropyrans as ligands for [Ru­(dppe) 2 R] + (where R = Cl or CCPh). , The trimethylsilyl-protected ethynylspiropyrans ( 7 – 10 ) were synthesized by the condensation of the respective indolinium salts ( 1 or 2 ) and salicylaldehydes ( 3 – 6 ) under basic conditions. − The terminal alkynes ( 11 – 14 ) were readily obtained by desilylation using Bu 4 NF in THF (Scheme ). , …”

“…The compounds 1 , 2 , 5 , 7 , 8 , 9 , 11 , 12 , 13 , 15 , 20 , and Fc­[PF 6 ] were synthesized according to existing literature procedures. All other reagents and materials were obtained from commercial suppliers and used as received.…”

“…36 The five-coordinate intermediate insertion products were not isolated because of their noted air sensitivity. 37−39 24 The fact that this peak manifests as an apparent singlet in the 31 P{ 1 H} NMR spectra for 16 and 17 is thought to be a result of coincidental equivalence of the chemical shifts in CD 2 Cl 2 . Switching to C 6 D 6 resulted in a clearer separation of the AB spin system (J PP = 14 Hz) for complex 19 but not 18, further evincing the diastereotopic nature of the phosphorus nuclei.…”

Functionalised organometallic photoswitches containing dihydropyrene units

“…[15][16][17] Organometallic moieties introduce functionality beyond that of the photochemical binary paradigm and offer convenient points for modelling charge transfer across bridging ligands due to the access to mixed-valence complexes. 18 Coordination complexes containing the DHP moiety have been synthesised and electrochemical assisted switching has been recognised. [19][20][21][22] The first report of a metal-alkynyl-DHP complex provided evidence of photochromic and redox switching of both the DHP moiety and metal.…”