A series of Ar-BIAN-based copper(I) complexes (where Ar-BIAN = bis(aryl)acenaphthenequinonediimine) were synthesised and characterised by (1)H and (13)C NMR spectroscopies, FT-IR spectroscopy, MALDI-TOF-MS spectrometry, cyclic voltammetry and single crystal X-ray diffraction. The bis-chelated complexes of general formula [Cu(Ar-BIAN)(2)]BF(4) (where Ar = C(6)H(5) (1), 4-iPrC(6)H(4) (3), 2-iPrC(6)H(4) (4)) were prepared by reaction of [Cu(NCMe)(4)]BF(4) with two equivalents of the corresponding Ar-BIAN ligands, in dichloromethane, while the mono-chelated complexes of the type [Cu(Ar-BIAN)L(2)]BF(4) (where Ar = 2,6-iPr(2)C(6)H(3), L = PhCN (6); Ar = 4-iPrC(6)H(4), L = PPh(3) (7)) were readily accessible by treatment of [Cu(NCR)(4)]BF(4) (R = Me, Ph) with one equivalent of the corresponding Ar-BIAN ligands in the absence or presence of two equivalents of PPh(3), in the same solvent. The structures of complexes 3, 4, 6 and 7 were obtained by single crystal X-ray diffraction, showing distorted tetrahedral geometries around the copper centres in all cases. The electrochemical studies of these complexes and of the already reported [Cu(2,4,6-Me(3)C(6)H(2)-BIAN)(2)]BF(4) (2) and [Cu(2,6-iPr(2)C(6)H(3)-BIAN)(NCMe)(2)] (5), demonstrated that the bis-chelated complexes 1-4 undergo a reversible one-electron reduction or oxidation processes on copper, while the mono-chelated complexes 5-7 show a partially reversible oxidation and an irreversible reduction feature. Both kinds of (Ar-BIAN)copper(I) complexes are active catalysts for the copper(I)-catalysed azide-alkyne cycloaddition reaction (CuAAC). Complex 7, bearing PPh(3) ligands, exhibits the highest catalytic activity, which is comparable with that of the typical CuSO(4)-sodium ascorbate catalyst system.
New bis- and tris(iminopyrrole)-functionalized linear (1,2-(HNC4 H3 -C(H)N)2 -C6 H4 (2), 1,3-(HNC4 H3 -C(H)N)2 -C6 H4 (3), 1,4-(HNC4 H3 -C(H)N)2 -C6 H4 (4), 4,4'-(HNC4 H3 -C(H)N)2 -(C6 H4 -C6 H4 ) (5), 1,5-(HNC4 H3 C-(H)N)2 -C10 H6 (6), 2,6-(HNC4 H3 C-(H)N)2 -C10 H6 (7), 2,6-(HNC4 H3 C-(H)N)2 -C14 H8 (8)) and star-shaped (1,3,5-(HNC4 H3 -C(H)N-1,4-C6 H4 )3 -C6 H3 (9)) π-conjugated molecules were synthesized by the condensation reactions of 2-formylpyrrole (1) with several aromatic di- and triamines. The corresponding linear diboron chelate complexes (Ph2 B[1,3-bis(iminopyrrolyl)-phenyl]BPh2 (10), Ph2 B[1,4-bis(iminopyrrolyl)-phenyl]BPh2 (11), Ph2 B[4,4'-bis(iminopyrrolyl)-biphenyl]BPh2 (12), Ph2 B[1,5-bis(iminopyrrolyl)-naphthyl]BPh2 (13), Ph2 B[2,6-bis(iminopyrrolyl)-naphthyl]BPh2 (14), Ph2 B[2,6-bis(iminopyrrolyl)-anthracenyl]BPh2 (15)) and the star-shaped triboron complex ([4',4'',4'''-tris(iminopyrrolyl)-1,3,5-triphenylbenzene](BPh2 )3 (16)) were obtained in moderate to good yields, by the treatment of 3-9 with B(C6 H5 )3 . The ligand precursors are non-emissive, whereas most of their boron complexes are highly fluorescent; their emission color depends on the π-conjugation length. The photophysical properties of the luminescent polyboron compounds were measured, showing good solution fluorescence quantum yields ranging from 0.15 to 0.69. DFT and time-dependent DFT calculations confirmed that molecules 10 and 16 are blue emitters, because only one of the iminopyrrolyl groups becomes planar in the singlet excited state, whereas the second (and third) keeps the same geometry. Compound 13, in which planarity is not achieved in any of the groups, is poorly emissive. In the other examples (11, 12, 14, and 15), the LUMO is stabilized, narrowing the gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO), and the two iminopyrrolyl groups become planar, extending the size of the π-system, to afford green to yellow emissions. Organic light-emitting diodes (OLEDs) were fabricated by using the new polyboron complexes and their luminance was found to be in the order of 2400 cd m(-2) , for single layer devices, increasing to 4400 cd m(-2) when a hole-transporting layer is used.
Reactions of 2-(N-arylimino)pyrroles (HNC4H3C(H)=N-Ar) with triphenylboron (BPh3) in boiling toluene afford the respective highly emissive N,N'-boron chelate complexes, [BPh2 {κ(2)N,N'-NC4H3C(H)=N-Ar}] (Ar=C6H5 (12), 2,6-Me2-C6H3 (13), 2,6-iPr2-C6H3 (14), 4-OMe-C6H4 (15), 3,4-Me2-C6 H3 (16), 4-F-C6H4 (17), 4-NO2-C6H4 (18), 4-CN-C6H4 (19), 3,4,5-F3-C6H2 (20), and C6F5 (21)) in moderate to high yields. The photophysical properties of these new boron complexes largely depend on the substituents present on the aryl rings of their N-arylimino moieties. The complexes bearing electron-withdrawing aniline substituents 17-20 show more intense (e.g., ϕf =0.71 for Ar=4-CN-C6H4 (19) in THF), higher-energy (blue) fluorescent emission compared to those bearing electron-donating substituents, for which the emission is redshifted at the expense of lower quantum yields (ϕf=0.13 and 0.14 for Ar=4-OMe-C6H4 (15) and 3,4-Me2-C6H3 (16), respectively, in THF). The presence of substituents bulkier than a hydrogen atom at the 2,6-positions of the aryl groups strongly restricts rotation of this moiety towards coplanarity with the iminopyrrolyl ligand framework, inducing a shift in the emission to the violet region (λmax =410-465 nm) and a significant decrease in quantum yield (ϕf=0.005, 0.023, and 0.20 for Ar=2,6-Me2-C6H3 (13), 2,6-iPr2-C6H3 (14), and C6F5 (21), respectively, in THF), even when electron-withdrawing groups are also present. Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations have indicated that the excited singlet state has a planar aryliminopyrrolyl ligand, except when prevented by steric hindrance (ortho substituents). Calculated absorption maxima reproduce the experimental values, but the error is higher for the emission wavelengths. Organic light-emitting diodes (OLEDs) have been fabricated with the new boron complexes, with luminances of the order of 3000 cd m(-2) being achieved for a green-emitting device.
Four sterically congested and highly electronically unsaturated bis(5-aryl-2iminopyrrolyl) ML 2 complexes of Fe(II) and Co(II), [M{κ 2 N,N-5-(2,6-R 2 -C 6 H 3 )-NC 4 H 2 -2-C(H)=N(2,6-i Pr 2 -C 6 H 3 )} 2 ] (M = Fe, R = H (1a); M = Fe, R = Me (1b); M = Co, R = H (2a); M = Co, R = Me (2b)), were synthesized by metathetic reaction of the in situ prepared sodium salts of the new 5-aryl-2-(N-2,6-diisopropylformimino)pyrrole HL type ligand precursors (R = H (Ia), Me (Ib)) with FeCl 2 or CoCl 2 , in moderate to good yields. The fourcoordinate complexes were characterized by elemental analysis, X-ray diffraction, magnetic susceptibility measurements in solution and in solid state, and 57 Fe Mössbauer spectroscopy.All complexes have a high-spin electronic configuration, as measured both in solution, through the Evans method, and in solid state, through SQUID magnetic measurements, and Mössbauer spectroscopy for the case of Fe(II) complexes, displaying a tetracoordinated distorted tetrahedral coordination geometry about the respective metal center, as elucidated by X-ray diffraction. The inclusion of ortho-methyl groups in the 5-phenyl substituent of the 2-iminopyrrolyl ring in complexes 1b and 2b has an important influence in the structure of the complexes, giving rise to pronounced geometry distortions in particular for 1b. This complex exhibits a see-saw-like geometry whereas a pyramidalization of the pyrrolyl nitrogen is observed for 2b. Overall, the magnetic properties of the complexes can be rationalized by taking into account the effect of the magnetic anisotropy arising from the second-order spin orbit coupling and the geometrical distortion. The simulation of the magnetic data using a zero-field splitting (ZFS) Hamiltonian led to values of the axial anisotropy, D, that are coherent for Co(II) and Fe(II) tetrahedral complexes, D ≈ -50 cm -1 (2a, 2b) and 4 cm -1 (1a). In the case of 1b the simulation evidenced a strong magnetic anisotropy with both axial and rhombic contributions (D ≈ -50 cm -1 , E ≈ 10 cm -1 ) which are in line with the strongly distorted coordination sphere of the complex.
Single-dose coffee capsules have revolutionized the coffee market, fueling espresso coffee popularity and offering access to a wide selection of coffee blends. Nevertheless, scarce information related to coffee powder and brew’s combined volatile characterization is available. In this study, it is hypothesized that coffee brew aroma characteristics can be predicted based on coffee powder’s volatile composition. For this, headspace solid-phase microextraction (HS-SPME) combined with comprehensive twodimensional gas chromatography with time-of-flight mass spectrometry detection (GC × GCToFMS) was used. The data were combined via chemometric tools to characterize in depth the volatile composition of eight blends of capsule-coffee powder and respective espresso brews, simulating the consumer’s perception. A total of 390 volatile compounds were putatively identified, 100 reported for the first time in roasted coffee or brews. Although the same chemical families were determined among the coffee powders and espresso brews, a different volatile profile was determined for each matrix. The Pearson correlation of coffee powders and respective brews allowed to identify 15 volatile compounds, mainly terpenic and esters recognized by their pleasant notes, with a strong relationship between the amounts present in both matrices. These compounds can be key markers to predict the volatile aroma potential of an espresso brew when analyzing the coffee powder.
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