1,3,5-Triäthyl- und 1,3,5-Triphenylborazinderivate

Meller, A.; Wechsberg, M.

doi:10.1007/bf00901373

Cited by 11 publications

(15 citation statements)

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“…1 H NMR (600 MHz, CDCl 3 , À50 8C): d = 7.29 (d, J = 7.32 Hz, 3 H; meso-Ph-ortho), 6.89 (d, J = 7.32 Hz, 6 H; b-Ph-ortho), 6.80 (t, J = 7.74 Hz, 3 H; meso-Ph-para), 6.78 (t, J = 6.90 Hz, 6 H; b-Ph-para), 6.72 (t, J = 7.32 Hz, 6 H; b-Ph-meta), 6.59 (t, J = 8.22 Hz, 3 H; meso-Ph-meta), 6.27 (br, 6 H; b-Ph-meta), 6. 24 (t,8.22 Hz,3 H; meso-Ph-meta), 6.09 (d, J = 6.90 Hz, 3 H; meso-Ph-ortho), 6.05 (d, J = 6.00 Hz, 6 H; b-Ph-ortho), 0.70 ppm (s, 3 H; axial-OMe); 11 B-and 13 C NMR spectra were not recorded because of poor solubility. UV/Vis (CH 2 Cl 2 ): l max (e) = 380 (200 000), 464 nm (26 000 m À1 cm À1 ); fluorescence (CH 2 Cl 2 , l ex = 374 nm): l max = 499, 528 nm; F F = 0.12; HR-ESI TOF-MS (positive mode): m/z: calcd for C 69 H 45 N 3 B 1 : 926.3712 [MÀOMe] + ; found: 926.3710.…”

Section: Pyridine-tri-n-pyrrolylborane (Ppb)mentioning

confidence: 99%

“…[1] This macrocycle has been long elusive despite its key position in porphyrin chemistry, however, since our first synthesis in 2006 [2] it has emerged as a promising functional pigment owing to its intense Soret-like absorption band, bright-green fluorescence, and aromaticity along the unique bent-bowl-shaped structure. The chemistry of subporphyrins contrasts sharply with that of subphthalocyanines, which has been continuously and extensively studied since their serendipitous synthesis by Meller and Ossko in 1972. [3,4] Although the attractive features of subporphyrins suggests they have promising potential, [5][6][7] the chemistry of subporphyrin still remains largely unexplored, due mainly to poorly developed synthetic methodology able to produce subporphyrins or to fabricate their peripheries.…”

Section: Introductionmentioning

confidence: 99%

“…The chemistry of subporphyrins contrasts sharply with that of subphthalocyanines, which has been continuously and extensively studied since their serendipitous synthesis by Meller and Ossko in 1972. [3,4] Although the attractive features of subporphyrins suggests they have promising potential, [5][6][7] the chemistry of subporphyrin still remains largely unexplored, due mainly to poorly developed synthetic methodology able to produce subporphyrins or to fabricate their peripheries. Herein we report the effective perbromination and subsequent coupling reactions of subporphyrins as the first peripheral fabrications of subporphyrins.…”

Section: Introductionmentioning

confidence: 99%

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Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso‐Aryl‐Substituted Subporphyrins

Tsurumaki

Inokuma

Easwaramoorthi

et al. 2008

Chemistry A European J

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Effective peripheral fabrication methods of meso-aryl-substituted subporphyrins were explored for the first time. Hexabrominated subporphyrins 2 were prepared quantitatively from the bromination of subporphyrins 1 with bromine. Hexaphenylated subporphyrins 3 and hexaethynylated subporphyrins 4 and 5 were synthesized by Suzuki-Miyaura coupling and Stille coupling, respectively, in good yields. X-ray crystal structures of 2 b, 3 b, 4 b, and 5 a revealed preservation of the bowl-shaped bent structures with bowl depths similar to that of 1. Hexaethynylated subporphyrins exhibit large two-photon-absorption cross-sections due to effective delocalization of the conjugated network to the ethynyl substituents.

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Section: Pyridine-tri-n-pyrrolylborane (Ppb)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso‐Aryl‐Substituted Subporphyrins

Tsurumaki

Inokuma

Easwaramoorthi

et al. 2008

Chemistry A European J

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“…In contrast to the corresponding chloro derivatives, fluorosubazaporphyrins are quite robust towards hydrolysis. All of the new compounds were characterized by several spectroscopic techniques, which included 1 H, 13 C, 19 F, 15 N, and 11 B NMR spectroscopy, IR spectroscopy, UV/Vis spectrophotometry, and mass spectrometry (both high and low resolution). In addition, DFT calcula-tions provided theoretical NMR spectroscopy values that are in good agreement with the experimental ones.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization, Molecular Structure and Theoretical Studies of Axially Fluoro‐Substituted Subazaporphyrins

Rodríguez‐Morgade

Claessens

Medina

et al. 2008

Chemistry A European J

128

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A new and general synthetic method for the preparation of fluoro‐substituted subazaporphyrins is reported that involves the treatment of the corresponding chloro‐ or aryloxy‐substituted subazaporphyrins (SubAPs) with BF3⋅OEt2. The strategy has been applied to both subphthalocyanines (SubPcs) and subporphyrazines (SubPzs). The yields were high for the latter, although low yields were obtained for the benzo derivatives. In contrast to the corresponding chloro derivatives, fluorosubazaporphyrins are quite robust towards hydrolysis. All of the new compounds were characterized by several spectroscopic techniques, which included 1H, 13C, 19F, 15N, and 11B NMR spectroscopy, IR spectroscopy, UV/Vis spectrophotometry, and mass spectrometry (both high and low resolution). In addition, DFT calculations provided theoretical NMR spectroscopy values that are in good agreement with the experimental ones. The high dipole moments exhibited by the fluorosubazaporphyrins as a result of the presence of a fluorine atom in an axial position are responsible for the spontaneous and singular supramolecular aggregation of the macrocycles in the crystalline state. The molecular and crystal structures of two one‐dimensional fluorine SubAPs, namely, a SubPc and a SubPz, are discussed. Molecules of the same class stack in alternating configurations along the c axis, which gives rise to columns that contain large numbers of monomers. SubPz 3 c forms aggregates with the macrocycles arranged in a parallel fashion with the BF bonds perfectly aligned within a column, whereas with SubPc 3 b the neighboring columns cause a commensurate sinusoidal distortion along the columns in the c direction, which prevents the alignment of the BF bonds. However, the most remarkable feature, common to both crystalline architectures, is the extremely short and unusual intermolecular F⋅⋅⋅N distances of the contiguous molecules, which are shorter than the sum of the corresponding van der Waals radii. Theoretical calculations have shown that these short distances can be explained by the existence of a cooperativity effect as the number of monomers included in the cluster increases.

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“…Subporphyrazine (SubPz) and subphthalocyanine (SubPc) are contracted tri-pyrrolic ring derivatives that bear 14 π-electrons with a bowl-shaped configuration. [1][2][3] SubPz and SubPc have been well studied since 1972 by Meller and Ossko, [4] and continually explored during the past years due to their potential applications related with their unique properties on nonlinear optics, [5,6] intramolecular energy-transfer process, [7,8] fluorescence-emission, [9] and intrinsic chirality. [10,11] Almost all the interesting properties of synthesized subporphyrin analogs rely on the tunable 14 π-electron conjugated macrocycles.…”

Section: Introductionmentioning

confidence: 99%

Periphery‐Hydrogenating Effects on the Unordinary 14 π‐Electron Delocalized Circuits and Related Electronic Properties of Subporphyrazine Analogs: A Density Functional Theory Investigation

Zhao

Xue

et al. 2012

Chin. J. Chem.

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Density functional theory method was employed to investigate the electronic properties of two series of subporphyrazine and subphthalocyanine derivatives, namely SubPz, SubPz-1H, SubPz-2H, SubPz-3H, SubPc, SubPc-1H, SubPc-2H, and SubPc-3H. Calculated results show that peripheral hydrogenation essentially changes the delocalized pattern from the common π 14 14 to limited π 13 14 or π 12 14 for SubPz series, and substantially weakens the aromaticity for both SubPz and SubPc compounds. The unordinary delocalized circuit owns an unstable energy level, and thus gives rise to a notable transformation of geometric configuration, frontier molecular orbital topology, and absorption spectral bands.Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) prove to be powerful methods to study electron density related properties and always give satisfactory accuracy on the calculating results of porphyrin-like conjugated systems. [20][21][22] Periphery-Hydrogenating Effects on the Unordinary 14 π-Electron Delocalized Circuits Chin.

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1,3,5-Triäthyl- und 1,3,5-Triphenylborazinderivate

Cited by 11 publications

References 0 publications

Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso‐Aryl‐Substituted Subporphyrins

Peripheral Hexabromination, Hexaphenylation, and Hexaethynylation of meso‐Aryl‐Substituted Subporphyrins

Synthesis, Characterization, Molecular Structure and Theoretical Studies of Axially Fluoro‐Substituted Subazaporphyrins

Periphery‐Hydrogenating Effects on the Unordinary 14 π‐Electron Delocalized Circuits and Related Electronic Properties of Subporphyrazine Analogs: A Density Functional Theory Investigation

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