Synthesis and Photophysical Properties of Trimetallic Acetylide Complexes with a 1,3,5-Triazine Core

Abstract

Treatment of 2,4,6-tris(4-bromophenyl)-1,3,5-triazine (2,4,6-(4-BrC6H4)3-1,3,5-C3N3)with HC⋮CSiMe3 in the presence of Pd(PPh3)4/CuI and NEt3 produces 2,4,6-[4-(Me3SiC⋮C)C6H4]3-1,3,5-C3N3, which reacts with Bu4NF to yield 2,4,6-[4-(HC⋮C)C6H4]3-1,3,5-C3N3. Reaction of 2,4,6-[4-(HC⋮C)C6H4]3-1,3,5-C3N3 with AuCl(PPh3) in the presence of NEt3 produces the gold acetylide complex 2,4,6-[4-((PPh3)AuC⋮C)C6H4]3-1,3,5-C3N3. Treatment of 2,4,6-[4-(HC⋮C)C6H4]3-1,3,5-C3N3 with cis-RuCl2(dppe)2/NaPF6 followed by NEt3 gives 2,4,6-[4-(Cl(dppe)2RuC⋮C)C6H4]3-1,3,5-C3N3, which reacts with p-HC⋮CC6H4R (R = OCH3, NO2) to give 2,4,6-[4-((4-RC6H4C⋮C)(dppe)2RuC⋮C)C6H4]3-1,3,5-C3N3. The electrochemical and photophysical properties of the new complexes have been investigated.

Long-distance electronic interaction in a molecular wire consisting of a ferrocenyl–ethynyl unit bridging two [(η5-C5H5)(dppe)M] metal centers

“…Binuclear complexes of 1-7 were prepared by reacting ferrocenylethynyl spacers (8)(9)(10)(11)(12) with stoichiometric amount of (g 5 -C 5 H 5 )(dppe)MCl. Complexes were purified by column chromatography and recrystallization.…”

“…Recently, the study of homo-and hetero-metallic binuclear transition metal complexes in which the end-capped metal centers are connected by p-conjugated organic linear spacers has been an intriguing area of research, since such system may provide the possibility to study the electronic coupling between the redox-active end-capped metal centers, or propose as models for molecular wires. In this context, end-capping of unsaturated organic spacers with various redox-active groups, such as ferrocene, ruthenium(II) polypyridine [4][5][6][7][8][9], [RuL 2 Cl] (L 2 = 2PPh 3 , Ph 2 PCH 2 CH 2 PPh 2 (dppe)) [10,11], and [M(g 5 -C 5 H 5 )L 2 ] (M = Fe(II), Ru(II), and Os(II)) metal centers [12][13][14][15][16][17][18][19][20][21], have been most studied where they are intended to promote the long-range electronic coupling. The nature of the end-capped metal center and p-conjugated organic spacer plays significantly important role in determining the magnitude of electronic coupling.…”

A simple synthesis of trans-RuCl(CCR)(dppe)2 complexes and representative molecular structures

“…The chemistry of transition metal complexes transRuCl(C"CR)(dppe) 2 is very well established [1][2][3][4][5][6][7][8][9][10], with a considerable body of recent research demonstrating the utility of these moieties in the construction of multimetallic complexes [11][12][13][14][15], optical materials [16][17][18], including those that exhibit pH or redox-switchable NLO response [19][20][21][22][23][24][25], colormetric [26] and fluorescent [27] sensing behaviour, the ''wire-like" behaviour that arises from extensive d-p mixing along the Ru-C"C fragment [28][29][30][31][32][33][34][35][36][37], and other characteristics that make these compounds potentially useful molecular electronic components [5,33,34,[38][39][40][41]. The facile replacement of the chloride ligand in complexes trans-RuCl(C"CR)(dppe) 2 either directly or from related vinylidenes with a second alkynyl ligand is well documented …”

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

“…In the emerging field of molecular electronics, polynuclear carbon-rich complexes featuring the electron-rich and redox-active organometallics endgroups [1][2][3] constitute very appealing materials for information storage and processing at the molecular level [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. From this point of view the understanding of electron transfer over nanometric distances in a single molecule constitutes an important objective.…”