Synthesis of Dibenzo[<i>b</i>,<i>f</i>]silepins with a Benzoquinolyl Ligand

Tokoro, Yuichiro; Tanaka, Kazuo; Chujo, Yoshiki

doi:10.1021/ol400730n

Cited by 17 publications

(7 citation statements)

References 61 publications

(21 reference statements)

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“…These two fundamental properties provide the formation of strong intra- and intermolecular hydrogen bonds both between the silanol molecules and with a large variety of organic molecules. Intramolecular hydrogen bonds in silanols have been studied by X-ray, Raman, IR, ,,,, and NMR spectroscopy, ,, as well as quantum chemistry. ,,,, NMR, FT-IR, and theoretical studies of various types of geminal silsesquioxane silanols showed that the formation of intra- and intermolecular hydrogen bonds O–H···O depends on both the medium effects and the steric and electronic effects of the substituents at silicon…”

Section: Introductionmentioning

confidence: 99%

Apicophilicity versus Hydrogen Bonding. Intramolecular Coordination and Hydrogen Bonds in N-[(Hydroxydimethylsilyl)methyl]-N,N′-propyleneurea and Its Hydrochloride. DFT and FT-IR Study and QTAIM and NBO Analysis

et al. 2014

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Conformers of N-[(hydroxydimethylsilyl)methyl]-N,N′-propyleneurea (1) and their hydrochlorides (2) with HCl coordinated to different basic sites have been studied experimentally by FT-IR and theoretically using the density functional theory (DFT) method at the B3LYP/6-311+G(d,p) and M06/6-311+G(d,p) levels of theory. The structures of silanols 1 and 2 are determined by the balance of two competing effects: namely, intramolecular CO→Si coordination and intramolecular C OThe preferred conformation of silanol 1 is that with an equatorial hydroxyl group, in apparent contradiction with the apicophilicity rule. In the crystal, silanol 1 exists as a conformer with a bifurcated bond composed of a weak CO→Si coordinated bond and a substantially more strong CO•••H−O hydrogen bond. From the NBO analysis, the energies of the n O → σ* Si−X and n O → σ* H−O orbital interactions responsible for the formation of the coordination and hydrogen bonds, as well as the lengths of these bonds, change in opposite directions. In solution the equilibrium is shifted toward the conformer having only the hydrogen bond and no coordination bond. Its hydrochloride 2 exists in the crystal as a conformer with the axial OH group coordinated to HCl, whereas in solution it appears to be in equilibrium with a conformer having the equatorial OH group, in which a four-centered bifurcated bond is formed by two intramolecular components CO→Si and CO•••HO and one intermolecular component CO•••HCl. The QTAIM analysis showed the O→Si coordination bonds in the studied compounds to fall in the range from partially covalent and weak donor−acceptor to mainly electrostatic in nature and the hydrogen bonds to vary from weak to medium in energy.

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Section: Introductionmentioning

confidence: 99%

Apicophilicity versus Hydrogen Bonding. Intramolecular Coordination and Hydrogen Bonds in N-[(Hydroxydimethylsilyl)methyl]-N,N′-propyleneurea and Its Hydrochloride. DFT and FT-IR Study and QTAIM and NBO Analysis

et al. 2014

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“…The emission spectra of dithienobismoles (73)(74)(75)(76) showed broad bands centered at 600-640 nm. The phosphorescence lifetimes and quantum yield of 74-76 were approximately τ = 2-6 μs and 0.2 %, respectively (Table 4).…”

Section: Sb-and Bi-containing π-Conjugated Compounds For Photophysica...mentioning

confidence: 99%

“…It is well known that replacing the bridgehead sp 3 -hybridized C atom of cycloheptatriene with the heteroatom produces compounds having the properties of heteroatom incorporated; as a result, these classes of compounds have received much attention recently. [75][76] Many studies have been done on heteropins, which have seven-membered heptatriene cores connected by a heteroatom rather than a sp 3 -hybridized carbon atom. [77][78] In this direction, Naka and co-workers substituted the bridgehead sp 3 C of dibenzocycloheptene by As atom to check its effect on the photoluminescence properties.…”

Section: Dibenzoarsepinsmentioning

confidence: 99%

“…Unlike π-conjugated organoarsenic compounds, the photophysical properties of π-conjugated Sb and Bi compounds are not that extensive. [22,18] Ohshita and Higashimura first reported the synthesis, and characterisation, of four dithienobismoles (73)(74)(75)(76) in 2010, and explored their utilities as phosphorescent materials. The reactions of dilithiobithiophenes with aryldihalobismuthanes, afforded corresponding dithienobismoles (73)(74)(75)(76) as shown in Scheme 14.…”

Section: Sb-and Bi-containing π-Conjugated Compounds For Photophysica...mentioning

confidence: 99%

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Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

et al. 2023

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Recent success in the synthesis of π-conjugated heavier pnictogen (As, Sb, and Bi) compounds and their transition metal complexes has led to the current surge in interest that led to significant development in the field of photophysical and optoelectronic properties of heavier pnictogens and their transition metal complexes. The presence of heavier pnictogens (As, Sb and Bi) in the molecular skeleton promotes inter-system crossing (ISC) and reverse inter-system crossing (RISC), because of the heavy atom effect, via altering the intermolecular interactions and orbital energy levels. As a result, π-conjugated heavier pnictogen compounds such as arsines, dibenzoarsepins, arsinoquinoline, heterofluorene, benzo[b]heterole (heterole = arsole, bismole, and stibole) show unique optoelectronic properties such as narrow bandgap, low-energy absorption, and long-wavelength emission than lighter pnictogen-based compounds. This review focuses on recent advances in the synthesis and photophysical properties of heavier pnictogen compounds. The synthesis and photophysical properties of heavier pnictogens are discussed and elaborated.

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“…Dibenzoheteropins (Scheme , I ) with saddle-shaped structures are more stable than heteropins. Moreover, dibenzoheteropins such as dibenzazepin (X = NR), dibenzoxepin (X = O), and dibenzosilepin (X = SiR 2 ) have been investigated in the development of new organic electronic materials. , Borepin, in which the 6π-electron 7-membered ring is planar and aromatic, is another class of boron-containing heteropins. A series of annulated borepins (Scheme , II ) including π-expanded fused borepins that contain two borepin rings have been reported by the groups of Yamaguchi, Piers, and Tovar .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of bis-BN-Naphthalene-Fused Oxepins and Their Photoluminescence Including White-Light Emission

Tian

Zhao

et al. 2019

J. Org. Chem.

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A series of novel bis-BN-naphthalene-fused oxepin derivatives were synthesized via a Pd-catalyzed tandem reaction from brominated 2,1-borazaronaphthalenes and cis-bis(boryl)alkenes. X-ray crystallographic analysis revealed that bis-BN-naphthalene-fused oxepins feature a planar framework. The electronic and photophysical properties of the novel BN-naphthalene-fused oxepins were investigated by UV–vis and fluorescence spectroscopies and density functional theory (DFT) calculations, which disclosed the distinct electronic and photophysical properties of the analogous hydrocarbon system. Interestingly, dual-fluorescent emissions were observed upon dissolving N-substituted derivatives 10–14 in dimethyl sulfoxide. Tunable emission colors especially for white-light emissions can be achieved by controlling the ratio of solvents, concentration, or temperature using only a single-molecule compound.

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Synthesis of Dibenzo[b,f]silepins with a Benzoquinolyl Ligand

Abstract: A benzo[h]quinolyl ligand provided pentacoordinate character for silicon in dibenzo[b,f]silepins. Substituents on the silicon center determined both conformations of the dibenzosilepin and luminescence properties in relation to charge transfer.

Cited by 17 publications

References 61 publications

Apicophilicity versus Hydrogen Bonding. Intramolecular Coordination and Hydrogen Bonds in N-[(Hydroxydimethylsilyl)methyl]-N,N′-propyleneurea and Its Hydrochloride. DFT and FT-IR Study and QTAIM and NBO Analysis

Apicophilicity versus Hydrogen Bonding. Intramolecular Coordination and Hydrogen Bonds in N-[(Hydroxydimethylsilyl)methyl]-N,N′-propyleneurea and Its Hydrochloride. DFT and FT-IR Study and QTAIM and NBO Analysis

Synthesis and Photophysical Properties of Heavier Pnictogen Complexes

Synthesis of bis-BN-Naphthalene-Fused Oxepins and Their Photoluminescence Including White-Light Emission

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