The relevance of the fluorine interactions in the supramolecular structure of a complex constructed from copper(II) hexafluoroacetylacetonate and the 4′-(3-pyridyl)-2,2′:6′,2″-terpyridine ligand. Novel C–F/π synthons involving the π-system of the terpyridine moieties and those of the hexafluoroacetylacetonate chelate rings

Granifo, Juan; Toledo, Dominique; Garland, Marı́a Teresa; Baggio, Ricardo

doi:10.1016/j.jfluchem.2009.10.016

Cited by 9 publications

(2 citation statements)

References 35 publications

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“…7). The face-to-face contact is between a fluorophenyl ring and one pyridine ring of a bpy ligand; the rings are slipped such that the F atom lies partly over the pyridine π-system 48,49 (Fig. 7b) and the interplane angle is 12.4°.…”

Section: Synthesis and Characterization Of [Ir(c^n) 2 (Bpy)][pf 6 ] Cmentioning

confidence: 99%

Green-emitting iridium(iii) complexes containing sulfanyl- or sulfone-functionalized cyclometallating 2-phenylpyridine ligands

et al. 2014

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A series of [Ir(C^N)2(bpy)][PF6] complexes in which the cyclometallating ligands contain fluoro, sulfane or sulfone groups is reported. The conjugate acids of the C^N ligands in the complexes are 2-(4-fluorophenyl)pyridine (H1), 2-(4-methylsulfonylphenyl)pyridine (H3), 2-(4-(t)butylsulfanylphenyl)pyridine (H4), 2-(4-(t)butylsulfonylphenyl)pyridine (H5), 2-(4-(n)dodecylsulfanylphenyl)pyridine (H6), 2-(4-(n)dodecylsulfonylphenyl)pyridine (H7). The single crystal structures of H3 and H5 are described. [Ir(C^N)2(bpy)][PF6] with C^N = 1, 3, 4, 5 and 7 were prepared from the appropriate [Ir2(C^N)4Cl2] dimer and bpy; the structure of [Ir2(3)4Cl2]·2CH2Cl2 was determined. [Ir(6)2(bpy)][PF6] was prepared by nucleophilic substitution starting from [Ir(1)2(bpy)][PF6]. The [Ir(C^N)2(bpy)][PF6] complexes have been characterized by NMR, IR, absorption and emission spectroscopic and mass spectrometric methods. The single crystal structures of enantiomerically pure Δ-[Ir(1)2(bpy)][PF6] and of rac-4{[Ir(1)2(bpy)][PF6]}·Et2O·2CH2Cl2 are described, and the differences in inter-cation packing in the structures compared. [Ir(1)2(bpy)][PF6], [Ir(4)2(bpy)][PF6] and [Ir(6)2(bpy)][PF6] (fluoro and sulfane substituents) are yellow emitters (λ(em)(max) between 557 and 577 nm), and the room temperature solution emission spectra are broad. The sulfone derivatives [Ir(3)2(bpy)][PF6], [Ir(5)2(bpy)][PF6] and [Ir(7)2(bpy)][PF6] are green emitters and the emission spectra are structured (λ(em)(max) = 493 and 523 to 525 nm). High photoluminescence quantum yields (PLQYs) of 64-74% are observed for the sulfone complexes in degassed solutions. The emission lifetimes for the three complexes containing sulfone substituents are an order of magnitude longer (2.33 to 3.36 μs) than the remaining complexes (0.224 to 0.528 μs). Emission spectra of powdered solid samples have also been recorded; the broad emission bands have values of λ(em)(max) in the range 532 to 558 nm, and PLQYs for the powdered compounds are substantially lower (≤23%) than in solution. Trends in the redox potentials for the [Ir(C^N)2(bpy)][PF6] complexes are in accord with the observed emission behaviour.

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Section: Synthesis and Characterization Of [Ir(c^n) 2 (Bpy)][pf 6 ] Cmentioning

confidence: 99%

Green-emitting iridium(iii) complexes containing sulfanyl- or sulfone-functionalized cyclometallating 2-phenylpyridine ligands

et al. 2014

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“…In recent years, a new molecular recognition motif, namely, the lone-pair···π interaction, has been considered extremely important in the context of supramolecular recognition . This lone pair can come from a fluorine atom and interact with any electrophilic center.…”

Section: Supramolecular Chemistry In Organofluorine Compounds: Past A...mentioning

confidence: 99%

Is Organic Fluorine Really “Not” Polarizable?

Chopra

2012

Crystal Growth & Design

134

103

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The covalent chemistry of the main group element fluorine is well understood. In contrast, its noncovalent chemistry, which forms the pillar of the paradigm of supramolecular chemistry, is still in its infancy. The latter involves a complete understanding of the different interactions (both intermolecular and intramolecular) involving donor and acceptor atoms. This perspective highlights the recent developments in the understanding of noncovalent interactions in relation to organic fluorine (partially fluorinated compounds) and the versatility and importance of such interactions to the scientific community.

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Decorating Tetrathiafulvalene (TTF) with Fluorinated Phenyls through Sulfur Bridges: Facile Synthesis, Properties, and Aggregation through Fluorine Interactions

Sun

Liu

et al. 2014

Chemistry A European J

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Tetrathiafulvalene derivatives (TTF1-TTF9) bearing fluorinated phenyl groups attached through the sulfur bridges have been synthesized by employing a copper-mediated C-S coupling reaction of C6 H5-x Fx I (x=1, 2, 5) and a zinc-thiolate complex, (TBA)2 [Zn(DMIT)2 ] (TBA=tetrabutyl ammonium, DMIT=1,3-dithiole-2-thione-4,5-dithiolate), as the key step. Particularly, the selective synthesis of C6 F5 -substituted (TTF8) and C6 F4 -fused (TTF9) TTFs from C6 F5 I is disclosed. The physicochemical properties and crystal structures of these TTFs are fully investigated by UV/Vis absorption spectra, cyclic voltammetry, molecular orbital calculation, and single-crystal X-ray diffraction. The exchange of hydrogen versus fluorine on the peripheral phenyl groups show a notable influence on both the electronic and crystallographic natures of the resulting TTFs: 1) lowering both the HOMO and the LUMO energy levels, 2) modulating the electrochemical properties by regioselective and/or the degree of fluorination, 3) enhancing the driving forces of stacking by multiple fluorine interactions (F⋅⋅⋅S, CF⋅⋅⋅π/πF , CF⋅⋅⋅FC, and CF⋅⋅⋅H). This work indicates that the decoration with fluorinated phenyls holds promise to produce functional TTFs with novel electronic and aggregation features.

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Cited by 9 publications

References 35 publications

Green-emitting iridium(iii) complexes containing sulfanyl- or sulfone-functionalized cyclometallating 2-phenylpyridine ligands

Green-emitting iridium(iii) complexes containing sulfanyl- or sulfone-functionalized cyclometallating 2-phenylpyridine ligands

Is Organic Fluorine Really “Not” Polarizable?

Decorating Tetrathiafulvalene (TTF) with Fluorinated Phenyls through Sulfur Bridges: Facile Synthesis, Properties, and Aggregation through Fluorine Interactions

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