Photoinduced iron–cyclopentadienyl (Fe–Cp) bond cleavage reactions and photocontrolled polymerizations of strained [1]ferrocenophanes

Ieong, Nga Sze; Manners, Ian

doi:10.1016/j.jorganchem.2007.11.058

Cited by 14 publications

(6 citation statements)

References 41 publications

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“…). They are attributed to a Fe‐Cp bond dissociation as already proposed . Under identical light irradiation conditions, DC 1200 exhibits a faster bleaching than the two iodonium salts.…”

Section: Resultssupporting

confidence: 67%

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Mokbel

Toufaily

Hamieh

et al. 2015

J of Applied Polymer Sci

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Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one-component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms.

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“…). They are attributed to a Fe‐Cp bond dissociation as already proposed . Under identical light irradiation conditions, DC 1200 exhibits a faster bleaching than the two iodonium salts.…”

Section: Resultssupporting

confidence: 67%

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Mokbel

Toufaily

Hamieh

et al. 2015

J of Applied Polymer Sci

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“…[3] Among them, topologically simplest are metallohaptotropic arrays in which a single metal moiety photomigrates, thermally reversibly, to a higher-energy position along a fused p framework, without the assistance of additives. [4] Only two such systems are known, [Mo(PMe 3 ) 3 ] complexes of indole and quinazoline, discovered as part of a study focusing on catalytic hydrogenations of heterocycles. [5] We report 1) the photothermal reversibility of {CpCo} complexes of linear phenylenes [6] by a novel mode of haptotropism, namely, h 4 :h 4 from one cyclobutadiene ring to another (Scheme 1); 2) the first X-ray structures of metalated linear phenylenes, illustrating the aromatization of the ligand on complexation; 3) mechanistic aspects of the isomerization cycles; and 4) a DFT study providing a detailed picture of how the {CpCo} unit moves across the arene separating the two cyclobutadiene rings.…”

mentioning

confidence: 99%

Photo–Thermal Haptotropism in Cyclopentadienylcobalt Complexes of Linear Phenylenes: Intercyclobutadiene Metal Migration

et al. 2009

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An attractive strategy for achieving solar-thermal energy conversion is to harvest sunlight in the form of activated chemical bonds through photoisomerization of a suitable molecule that can release, on demand, such stored and transportable energy by thermal reversal to its original form.[1] When such reversible isomerizations entail significant topological alterations, they provide blueprints for eliciting further functions, for example in switches, machines, datastorage, sensors, and other devices. [1,2] Because of their expanded tunability and generally favourable electronic absorption regimes, organometallic complexes are advantageous in this respect, yet have remained relatively unexplored.[3] Among them, topologically simplest are metallohaptotropic arrays in which a single metal moiety photomigrates, thermally reversibly, to a higher-energy position along a fused p framework, without the assistance of additives.[4] Only two such systems are known, [Mo(PMe 3 ) 3 ] complexes of indole and quinazoline, discovered as part of a study focusing on catalytic hydrogenations of heterocycles. [5] We report 1) the photothermal reversibility of {CpCo} complexes of linear phenylenes [6] by a novel mode of haptotropism, namely, h 4 :h 4 from one cyclobutadiene ring to another (Scheme 1); 2) the first X-ray structures of metalated linear phenylenes, illustrating the aromatization of the ligand on complexation; 3) mechanistic aspects of the isomerization cycles; and 4) a DFT study providing a detailed picture of how the {CpCo} unit moves across the arene separating the two cyclobutadiene rings.The new complexes, 2, 5, and 6-8, were made from the respective 2,3,6,9-tetraethynyl linear [3]phenylene, 1,2,4,5-tetraethynylbenzene, and 2,3-diethynylbiphenylene ([D 2 ] for 8) synthons and their cocyclization with bis(trimethylsilyl)-acetylene (BTMSA) in the presence of stoichiometric [CpCo(CO) 2 ] (MeCp for 7), a strategy employed previously Scheme 1. Photo-thermal cycles of CpCo-phenylene complexes.

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“…First reported by Manners and co-workers in 1992, [ 117 ] ring-opening polymerization (ROP) of strained ring-tilted metallophanes ( 71 ) affords low-to-high molecular weight sandwich complex-containing macromolecules under conditions that range from living to non-living, controlled to uncontrolled polymerizations (Scheme 10 ). In ROP, the strained bond is broken under various mechanistic routes that include thermal, [ 57,[118][119][120][121][122] anionic, [123][124][125][126][127][128] cationic, [129][130][131] photolytic, [132][133][134][135][136][137] transition metal catalysis, [138][139][140][141][142] as well as ring-opening metathesis polymerization (ROMP) [143][144][145] to afford sandwich complexcontaining polymers. The mechanistic route can affect microscopic properties such as the architecture and molecular weight of the polymer.…”

Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

“…The versatility of ROP is also evident from the numerous spacers that can be incorporated in the polymeric main chain through this technique. These spacers that include single atom spacers such as Si, [ 41,134,135,140,[148][149][150][151][152] P, [ 127,[153][154][155][156][157][158][159] B, [ 139,160 ] Sn, [ 141,152,161 ] S, [ 162 ] Ge, [ 125,163 ] Ga, [ 60,164 ] Al, [ 60 ] Se; [ 162 ] two-atom spacers such as C-C, [ 122,136,145,147 ] C-P, [ 129 ] C-Si, [ 129 ] C-S, [ 129 ] C-Ge, [ 165 ] C-Sn; [ 165 ] as well as a four-atom butadienylene spacer, [ 144 ] affect the properties of macromolecules. For instance, reaction of dilithioferrocene ( 90 ) with the gallium dichloride ( 91 ) yielded the strained gallium-bridged ferrocenophane ( 92 ), which spontaneously underwent ROP to afford the poly(ferrocenylgallane) ( 93 ) (Scheme 17 ).…”

Section: Macromolecules Bearing Sandwich Complexes In the Main Chainmentioning

confidence: 99%

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

Abd‐El‐Aziz

Agatemor

Etkin

2014

Macromol. Rapid Commun.

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Sandwich complexes feature unique properties as the physical and electronic properties of a hydrocarbon ligand or its derivative are integrated into the physical, electronic, magnetic, and optical properties of a metal. Incorporation of these complexes into macromolecules results in intriguing physical, electrical, and optical properties that were hitherto unknown in organic-based macromolecules. These properties are tunable through well-designed synthetic strategies. This review surveys many of the synthetic approaches that have resulted in tuning the properties of sandwich complex-containing macromolecules. While the past two decades have seen an ever-growing number of research publications in this field, gaps remain to be filled. Thus, we expect this review to stimulate research interest towards bridging these gaps, which include the insolubility of some of these macromolecules as well as expanding the scope of the sandwich complexes.

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Photoinduced iron–cyclopentadienyl (Fe–Cp) bond cleavage reactions and photocontrolled polymerizations of strained [1]ferrocenophanes

Cited by 14 publications

References 41 publications

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Photo–Thermal Haptotropism in Cyclopentadienylcobalt Complexes of Linear Phenylenes: Intercyclobutadiene Metal Migration

Sandwich Complex‐Containing Macromolecules: Property Tunability Through Versatile Synthesis

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