Structural effects in the electron absorptio and luminescence spectra of decaborane(14) derivatives B10H12L2

Il’inchik, E. A.; Волков, В. В.; Dunaev, S. T.

doi:10.1007/bf02578570

Cited by 5 publications

(5 citation statements)

References 6 publications

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“…Although by itself decaborane ( 1 ) is non-luminescent, luminescence has been observed in borane-containing materials, including in conjunction with aromatic ligands (L) as in, for example, B 10 H 12 L 2 and B 18 H 20 L 2 octadecaborane derivatives. − The related macropolyhedral borane, anti -B 18 H 22 , which is nominally derived by the fusion of two nido -decaboranyl(14) units, as in Scheme , is also a highly fluorescent species with quantum yields of almost unity for the conversion of UVA irradiation into 410 nm blue light. ,, …”

Section: Resultsmentioning

confidence: 99%

Direct Phenylation of nido-B₁₀H₁₄

et al. 2022

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As a preliminary step toward its condensation into the porous polymer Activated Borane, the thermolysis of nido-B10H14 (1) in benzene at 200 °C results in the generation of a number of phenylated borane molecular species. The principal product is the new monophenylated compound 5-Ph-nido-B10H13 (2), isolated in 48% yield (based on consumption of 1) and structurally characterized by single-crystal X-ray diffraction analysis, NMR, and mass spectrometry along with other minor products, such as 6-Ph-nido-B10H13 (3), for which we observe UV-light-driven conversion into 2 via a “vertex-flip” mechanism, and novel diphenylated 5,8-Ph2-nido-B10H12 (4). Together, the phenylated derivatives provide a valuable insight into the assembly of Activated Borane and ultimately inform on its structure. The new compounds also display strong blue fluorescence in both solid-state and in solution and are the first examples of the direct phenylation of nido-B10H14, thus opening the door to the straight-forward synthesis of highly luminescent organic-borane hybrid systems.

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Section: Resultsmentioning

confidence: 99%

Direct Phenylation of nido-B₁₀H₁₄

et al. 2022

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“…The relevant CASSCF natural orbitals involved in the S0 → S1 and S0 → S2 transitions are shown in Figure 12 (see Supporting Information SI 12 for full listing of orbitals). Once again, as is seemingly becoming the rule for borane-pyridine systems, albeit in the limited number of studies so far reported, 28,46 there are charge-transfer transitions of in→out character, with promotion from the B1 orbital, which is mainly located on the boron cluster, to the π1* orbital (in the case of S0 → S2) or to the π2* orbital (in the case of S0 → S1), both of which are delocalized solely over the pyridine ligand (see Figure 12). Both S1 and S2 states are thus of the same nature, with the π2* and the π1* orbitals being the symmetric and anti-symmetric combination, respectively, of the * orbitals of the aromatic rings.…”

Section: State / Geometrymentioning

confidence: 93%

Substitution of the laser borane anti-B₁₈H₂₂ with pyridine: a structural and photophysical study of some unusually structured macropolyhedral boron hydrides

et al. 2018

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Reaction of anti-BH1 with pyridine in neutral solvents gives sparingly soluble BH-3',8'-Py3a as the major product (ca. 53%) and BH-6',9'-Py2 (ca. 15%) as the minor product, with small quantities of BH-8'-Py 4 (ca. 1%) also being formed. The three new compounds 2, 3a and 4 are characterized by single-crystal X-ray diffraction analyses and by multinuclear multiple-resonance NMR spectroscopy. Compound 2 is of ten-vertex nido:ten-vertex arachno two-atoms-in-common architecture, long postulated for a species with borons-only cluster constitution, but previously elusive. Compound 3a is of unprecedented ten-vertex nido:eight-vertex arachno two-atoms-in-common architecture. The single-crystal X-ray diffraction analysis for the picoline derivative BH(NCHMe)3b, similarly obtained, is also presented. BHPy 4 is also previously unreported but is of known ten-vertex nido:ten-vertex nido two-atoms-in-common architecture of anti configuration, but now with the pyridine ligand positioned differently to other reported examples of BHL compounds. Factors behind the remarkably low solubility of 3a and 3b are elucidated in terms of electrostatic potential (ESP) calculations, polarity, and van der Waals complementarities. In view of contemporary developing high interest in the fluorescent properties of macropolyhedral boron-containing species, a detailed assessment of the photophysical characteristics of 3a and 4 is also presented. In contrast to the thermochromic fluorescence of 2 (from 620 nm brick-red at room temperature to 585 nm yellow at 8 K, quantum yield 0.15), compound 3a is only weakly phosphorescent in the yellow region (590 nm, quantum yield 0.01), whereas compound 4 exhibits no luminescence. The far more photoactive nature of compound 2 is associated with S excited-state minima structures that differ from each other only by the relative rotational positions of the pyridine substituents on its disubstituted ten-vertex {arachno-BPy}-subcluster. The wavelength and relative intensity of fluorescence from these structures depends on the rotational positions of the pyridine ligands, which in turn are influenced by temperature and/or rotational inhibition in the solid-state.

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“…It should be noted that the reaction of decaborane( 14) with pyridine at low temperatures was found to form the 6,6-bis(pyridinium) derivative [arachno-6,6-Py2-B10H12], which, upon refluxing in dry degassed pyridine, converts into the more stable 6,9isomer (Scheme 5) [268]. All compounds of this series are brightly colored from yellow to red, which is the reason for the interest in their study by UV and luminescent spectroscopy [229,[271][272][273]. The 6,9bis(pyridinium) derivative [6,9-Py 2 -B 10 H 12 ] was studied by X-ray photoelectron and X-ray fluorescence spectroscopy [225,226] and, its diamagnetic susceptibility was determined [227].…”

Section: Derivatives With a B-n Bondmentioning

confidence: 99%

“…The thermal decomposition of the 6,9-bis(pyridinium) and 6,9-bis(quinolinium) derivatives was studied [274] [269] were determined by singlecrystal X-ray diffraction (Figure 17). All compounds of this series are brightly colored from yellow to red, which is the reason for the interest in their study by UV and luminescent spectroscopy [229,[271][272][273]. The 6,9-bis(pyridinium) derivative [6,9-Py2-B10H12] was studied by X-ray photoelectron and X-ray fluorescence spectroscopy [225,226] and, its diamagnetic susceptibility was determined [227].…”

Section: Derivatives With a B-n Bondmentioning

confidence: 99%

Decaborane: From Alfred Stock and Rocket Fuel Projects to Nowadays

Sivaev

2023

Molecules

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The review covers more than a century of decaborane chemistry from the first synthesis by Alfred Stock to the present day. The main attention is paid to the reactions of the substitution of hydrogen atoms by various atoms and groups with the formation of exo-polyhedral boron–halogen, boron–oxygen, boron–sulfur, boron–nitrogen, boron–phosphorus, and boron–carbon bonds. Particular attention is paid to the chemistry of conjucto-borane anti-[B18H22], whose structure is formed by two decaborane moieties with a common edge, the chemistry of which has been intensively developed in the last decade.

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Structural effects in the electron absorptio and luminescence spectra of decaborane(14) derivatives B10H12L2

Cited by 5 publications

References 6 publications

Direct Phenylation of nido-B₁₀H₁₄

Direct Phenylation of nido-B₁₀H₁₄

Substitution of the laser borane anti-B₁₈H₂₂ with pyridine: a structural and photophysical study of some unusually structured macropolyhedral boron hydrides

Decaborane: From Alfred Stock and Rocket Fuel Projects to Nowadays

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Structural effects in the electron absorptio and luminescence spectra of decaborane(14) derivatives B10H12L2

Cited by 5 publications

References 6 publications

Direct Phenylation of nido-B10H14

Direct Phenylation of nido-B10H14

Substitution of the laser borane anti-B18H22 with pyridine: a structural and photophysical study of some unusually structured macropolyhedral boron hydrides

Decaborane: From Alfred Stock and Rocket Fuel Projects to Nowadays

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Direct Phenylation of nido-B₁₀H₁₄

Direct Phenylation of nido-B₁₀H₁₄

Substitution of the laser borane anti-B₁₈H₂₂ with pyridine: a structural and photophysical study of some unusually structured macropolyhedral boron hydrides