Optical and electrochemical properties of spirobifluorene iridanaphthalene complexes

Talavera, María; Pereira-Cameselle, Raquel; Peña‐Gallego, Ángeles; Vázquez-Carballo, Irene; Prieto, Inmaculada; Alonso‐Gómez, José Lorenzo; Bolaño, Sandra

doi:10.1039/d2dt03465d

Cited by 4 publications

(6 citation statements)

References 43 publications

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“…propargyl groups to render a dimetallaaromatic SBF. 27 Remarkably, both systems present thermal stabilities above 200 C and a remarkable red shift compared with bare SBF.…”

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 92%

“…F I G U R E 7 Representation of chiral SBFs developed for surface functionalization. 23 F I G U R E 8 Schematic representation of SBF iridacycle 25 and SBF metallaaromatic systems 26,27 Cp* = 1,2,3,4,5pentamethylcyclopentadienyl; Mes = mesityl.…”

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 99%

“… 25 In order to drive the reaction to metallaaromatic formation over the SBF unit, the methyl group of the propargyl precursor was replaced by a mesityl group 26 . The same methodology was applied to an SBF substituted with two propargyl groups to render a dimetallaaromatic SBF 27 . Remarkably, both systems present thermal stabilities above 200°C and a remarkable red shift compared with bare SBF.…”

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 99%

“…Schematic representation of SBF iridacycle 25 and SBF metallaaromatic systems 26,27 Cp* = 1,2,3,4,5‐pentamethylcyclopentadienyl; Mes = mesityl.…”

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 99%

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Development of robust chiroptical systems through spirobifluorenes

Portela‐Pino,

Talavera,

Chiussi

et al. 2023

Chirality

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Chiroptical responses are valuable for the structural determination of dissymmetric molecules. However, the development of everyday applications based on chiroptical systems is yet to come. We have been earlier using axially chiral allenes for the construction of linear, cyclic, and cage‐shaped molecules that present remarkable chiroptical responses. Additionally, we have developed chiral surfaces through upstanding chiral architectures. Since the goal is to obtain robust chiroptical materials, more recently we have been studying spirobifluorenes (SBFs), a well‐established building block in optoelectronic applications. After theoretical and experimental demonstration, the suitability of chiral SBFs for the development of robust chiroptical systems was certified by the construction all‐carbon double helices, flexible shape‐persistent macrocycles, chiral frameworks for surface functionalization, and structures featuring helical or spiroconjugated molecular orbitals. Here, we give an overview of our contribution to these matters.

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“…propargyl groups to render a dimetallaaromatic SBF. 27 Remarkably, both systems present thermal stabilities above 200 C and a remarkable red shift compared with bare SBF.…”

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 92%

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 99%

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 99%

“…Schematic representation of SBF iridacycle 25 and SBF metallaaromatic systems 26,27 Cp* = 1,2,3,4,5‐pentamethylcyclopentadienyl; Mes = mesityl.…”

Section: Metallaaromatic Spirobifluorenesmentioning

confidence: 99%

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Development of robust chiroptical systems through spirobifluorenes

Portela‐Pino,

Talavera,

Chiussi

et al. 2023

Chirality

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“…Its origins go back to 1982, when Roper’s group provided experimental evidence for the theoretical prediction of the existence of aromatic metallacycles, made by Thorn and Hoffmann in 1979, with the preparation of the first osmabenzene . Since then, a wide range of aromatic species of this class have been isolated, mainly metallahydrocarbons and, to a lesser extent, metallaheterocycles and metalladiheterocycles . As a consequence of the effort, the field has now reached a remarkable degree of conceptual maturity …”

Section: Introductionmentioning

confidence: 99%

Preparation, Aromaticity, and Bromination of Spiro Iridafurans

Esteruelas,

Leon,

Moreno-Blázquez

et al. 2023

Inorg. Chem.

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Iridium centers of [Ir(μ-Cl)(C 8 H 14 ) 2 ] 2 (1) activate the C β (sp 2 )−H bond of benzylideneacetone to give [Ir(μ-Cl){κ 2 -C,O-[C(Ph)CHC(Me)O]} 2 ] 2 (2), which is the starting point for the preparation of the spiro iridafurans IrCl{κ 2 -C,O-[C(Ph)CHC-(Me)O]} 2 (P i Pr 3 ) (3), [Ir{κ 2 -C,O-[C(Ph)CHC(Me)-O]} 2 (MeCN) 2 ]BF 4 (4), [Ir(μ−OH){κ 2 -C,O-[C(Ph)CHC(Me)-O]} 2 ] 2 (5), Ir{κ 2 -C,O-[C(Ph)CHC(Me)O]} 2 {κ 2 -C,N-[C 6 MeH 3py]} (6), and Ir{κ 2 -C,O-[C(Ph)CHC(Me)O]} 2 {κ 2 -O,O-[acac]} (7). The five-membered rings are orthogonally arranged with the oxygen atoms in trans in an octahedral environment of the iridium atom. Spiro iridafurans are aromatic. The degree of aromaticity and the negative charge of the CH-carbon of the rings depend on ligand trans to the carbon directly attached to the metal. Aromaticity has been experimentally confirmed by bromination of iridafurans with N-bromosuccinimide (NBS). Reactions are sensitive to the degree of aromaticity of the ring and the negative charge of the attacked CH-carbon. Iridafurans can be selectively brominated, when different ligands lie trans to metalated carbons. Bromination of 3 occurs in the ring with the metalated carbon trans to chloride, whereas the bromination of 6 takes place in the ring with the metalated carbon trans to pyridyl. The first gives IrCl{κ 2 -C,O-[C(Ph)CBrC(Me)O]}{κ 2 -C,O-[C(Ph)CHC(Me)O]}(P i Pr 3 ) (8), which reacts with more NBS to form IrCl{κ 2 -C,O-[C(Ph)CBrC(Me)O]} 2 (P i Pr 3 ) (9). The second yields Ir{κ 2 -C,O-[C(Ph)CBrC(Me)O]}{κ 2 -C,O-[C(Ph)CHC(Me)O]}{κ 2 -C,N-[C 6 MeH 3 -py]} (10). The origin of the selectivity is kinetic, with the rate-determining step of the reaction being the NBS attack. The activation energy depends on the negative charge of the attacked atom; a higher negative charge allows for a lower activation energy. Accordingly, complex 7 undergoes bromination in the acetylacetonate ligand, giving Ir{κ 2 -C,O-[C(Ph)CHC(Me)O]} 2 {κ 2 -O,O-[acacBr]} (11).

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