Syntheses and material applications of Ru(II)(bisphosphine)2 alkynyls

Bis-Alkynyl Complexes of Fe(III) Tetraaza Macrocycles─A Tale of Two Rings

“…19 Ru-alkynyl compounds have played key roles in both synthetic method development of metal alkynyls and demonstration of extensive conjugation along Ru-alkynyl backbones. 1,2,20,21 Facile electron delocalization both through an oligoyn-diyl between two Ru centers 22,23 and across a -C 2 -Ru-C 2 -unit 24 has been demonstrated via the mixed valency therein. The excellence of Ru alkynyls in mediating charge transfer has been further validated using single-molecule measurement.…”

“…Ru-alkynyl compounds have played key roles in both synthetic method development of metal alkynyls and demonstration of extensive conjugation along Ru-alkynyl backbones. ,,, Facile electron delocalization both through an oligoyn-diyl between two Ru centers , and across a -C 2 -Ru-C 2 - unit has been demonstrated via the mixed valency therein. The excellence of Ru alkynyls in mediating charge transfer has been further validated using single-molecule measurement. − The demonstration of Ru–Ru long-distance coupling through oligothienylethynyl bridges by Patra and co-workers is an interesting recent development. , The majority of the aforementioned Ru alkynyls are supported with soft ligands such as phosphines and cyclopentadienyls (Cp/Cp*).…”

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

“…However, the preparation of bis(alkynyl) complexes trans -[Ru(CCR)(CCR′)(dppe) 2 ] from mono(alkynyl) precursor complexes trans -[RuCl(CCR)(dppe) 2 ] is often complicated by ligand scrambling, resulting in mixtures of symmetric and unsymmetric products. 20 Synthetic strategies employed to avoid such complex mixtures include transmetallation, 82 the use of activated alkynyl ammine complexes, 80,83 and the addition of a strong, non-nucleophilic base to deprotonate vinylidene intermediates. 80,84–86…”

“…However, the preparation of bis(alkynyl) complexes trans-[Ru(CuCR)(CuCR′)(dppe) 2 ] from mono (alkynyl) precursor complexes trans-[RuCl(CuCR)(dppe) 2 ] is often complicated by ligand scrambling, resulting in mixtures of symmetric and unsymmetric products. 20 Synthetic strategies employed to avoid such complex mixtures include transmetallation, 82 the use of activated alkynyl ammine complexes, 80,83 and the addition of a strong, non-nucleophilic base to deprotonate vinylidene intermediates. 80,[84][85][86] The syntheses of the mono-metallic, bis(alkynyl) complexes SP-10 and SP-11 were achieved in good yield by reacting the vinylidene [9]OTf with the respective 5′-or 6-ethynyl spiropyran in the presence of NaPF 6 and NEt 3 (Scheme 3).…”

“…[15][16][17][18][19] Transition metal alkynyl complexes have proven to be versatile test beds for this diversification of properties associated with hybrid molecular switches. [20][21][22] Moreover, coupling organic photochromic switches with organometallic moieties allows access to multiple states beyond the binary paradigm, 21,23,24 and permits the interrogation and manipulation of electron and energy transfer pathways across molecular bridges. [25][26][27] To date, the advantages of hybrid organometallic switches have best been shown by incorporating carbon-rich ruthenium systems with photoswitchable dithienylethene (DTE) moieties.…”