o-Carborane-assisted Lewis acidity enhancement of triarylboranes

Huh, Jung Oh; Kim, Hyungjun; Lee, Kang Mun; Lee, Yoon Sup; Do, Youngkyu; Lee, Min Hyung

doi:10.1039/b918263b

Cited by 107 publications

(95 citation statements)

References 26 publications

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“…Table 2 shows the absorption wavelengths(), transition energies(E), oscillator strengths(f) and major contributions of all of the closed-shell systems. The calculated results show that the strong absorption values of systems 1, 2 and 3 are at 272.5, 264.2 and 269.7 nm, respectively, and these results are in good agreement with the experimental results reported by Lee et al [22] (270 nm for 1, 260 nm for 2 and 265 nm for 3). This suggests that PBE1PBE/6-31+G(d) is a good choice to investigate the absorption spectra in our study.…”

Section: Electronic Spectrumsupporting

confidence: 82%

“…RTAB″ represents reduced forms of RTAB consisting of 1″, 2″, 3″, 4″ and 5″. Among these models, 1, 2, 3 and 1′ have been experimentally synthesized with good thermal stabilities by Huh et al [22], while other compounds were designed to compare properties with system 1 in this study. The origin of the coordinate system is placed in the C(5) atom with the z-axis along the bonding orientation between the C(5) atom and the B(1) atom.…”

Section: Theoretical Methods and Calculation Modelsmentioning

confidence: 99%

mentioning

confidence: 99%

“…We have also studied closo-C 2 B 10 H 12 carborane with an aryl group from the perspective of its use as a novel substituent on the phenylene ring of TAB. It was found that not only it does the carborane enhance Lewis acidity by the formation of an electron deficient cage, but also it leads to high stabilization of the vacant p(B) for the TAB used in the experiment [22]. Although efforts over several decades in the NLO field have resulted in far-ranging studies on the design, synthesis, structure, reactivity and application of these materials, a number of strategies have also been extensively studied as a part of this progress [23].…”

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Quantum chemical studies on tuning the second-order nonlinear optical molecular switching of triarylborane derivatives

Sun

et al. 2012

Chin. Sci. Bull.

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In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the secondorder nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained by introducing different inductive electron groups into the phenylene ring of the TAB (RTAB, where R=2-C 6 H 5 -C 2 B 10 H 10 (1), R=F(2), R=Me(3), R=NO 2 (4), R=NH 2 (5)). The static first hyperpolarizabilities ( tot ) of the RTAB molecules can be switched by binding one F  to the boron center (RTAB′)or one-electron reduction (RTAB"). The DFT-FF calculations show that the  tot values of 2′, 3′ and 5′ decrease while those of 1′and 4′ increase compared with the values of their neutral molecules, which was attributed to the fact that the charge transfers of 2, 3 and 5 become smaller and those of 1 and 4 become larger by binding one F  ion to the boron center, according to time-domain DFT (TD-DFT) analysis. However, the incorporation of one electron enhances the second-order NLO properties of the RTAB molecules remarkably, especially for system 1. It is notable that the  tot value of reduced form 1″ is 508.69×1030 esu, i.e. about 578 times larger than that of system 1. Frontier molecular orbital (FMO) and natural bond orbital (NBO) analyses suggest that the reversal of the charge distribution between the neutral molecules and their reduced forms leads to low HOMO-LUMO energy gaps (E 0 ) and thus large  tot values for the reduced forms. Novel molecular materials with optimal nonlinear optical (NLO) properties are still in great demand because of their primary roles in applications in fields including optical communications and computation, optical switching and limiting, data storage and retrieval, and sensors [1-4]. Recently, triarylborane (TAB) and its derivatives have attracted increasing attention because of their strong photophysical properties, and have been making greater contributions in the fields of luminescence [5][6][7][8], optoelectronics (organic light-emitting diodes and electroluminescence (OLED/EL), nonlinear optical and two-photon absorption) [9][10][11][12], catalytic polymerization [13][14][15] and anion sensors [16][17][18], because their intriguing electronic structures come from the p  - conjugation through the vacant p-orbital on the boron atom (p(B)) [19,20]. It is well known that the molecular second-order NLO properties depend not only on the nature of the -conjugation but also on the strengths of the donor and acceptor groups [21]. Thus, in this report, we have introduced the conventional electron donor or acceptor substituent groups to the phenylene ring of the TAB to optimize its NLO properties. We have also studied closo-C 2 B 10 H 12 carborane with an aryl group from the perspective of its use as a novel substituent on the phenylene ring of TAB. It was found that not only it does the carborane enhance Lewis acidity by the formation of an electron deficient cage, but also it leads to high stabilization of the vacant p(B) for the TAB used in the experiment [22]. Al...

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Section: Electronic Spectrumsupporting

confidence: 82%

Section: Theoretical Methods and Calculation Modelsmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Quantum chemical studies on tuning the second-order nonlinear optical molecular switching of triarylborane derivatives

Sun

et al. 2012

Chin. Sci. Bull.

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“…It is notable that the K value is greater by one order of magnitude than that of Mes 3 B (K = 3.3(± 0.5) × 10 5 M −1 in THF) which has a similar steric environment around the boron center. 6,14 This result indicates that the introduction of pyridyl groups enhances fluorophilicity of triarylborane probably due to the extended conjugation, as well as the electron-withdrawing effect of pyridyl group.…”

Section: Synthesis and Fluoride Binding Properties Of Tris-pyridiniummentioning

confidence: 65%

Synthesis and Fluoride Binding Properties of Tris-pyridinium Borane

Lee¹,

Kim²,

Do³

et al. 2013

Bulletin of the Korean Chemical Society

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Ortho‐Carborane Decorated Multi‐Resonance TADF Emitters: Preserving Local Excited State and High Efficiency in OLEDs

Lee,

Jang,

Nguyen

et al. 2024

Advanced Science

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A novel class of o‐carboranyl luminophores, 2CB‐BuDABNA (1) and 3CB‐BuDABNA (2) is reported, in which o‐carborane moieties are incorporated at the periphery of the B,N‐doped multi‐resonance thermally activated delayed fluorescence (MR‐TADF) core. Both compounds maintain the inherent local emission characteristics of their MR‐emitting core, exhibiting intense MR‐TADF with high photoluminescence quantum yields in toluene and rigid states. In contrast, the presence of the dark lowest‐energy charge transfer state, induced by cage rotation in THF, is suggested to be responsible for emission quenching in a polar solvent. Despite the different arrangement of the cage on the DABNA core, both 1 and 2 show red‐shifted emissions compared to the parent compound BuDABNA (3). By utilizing 1 as the emitter, high‐efficiency blue organic light‐emitting diodes (OLEDs) are achieved with a remarkable maximum external quantum efficiency of 25%, representing the highest reported efficiency for OLEDs employing an o‐carboranyl luminophore as the emitter.

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o-Carborane-assisted Lewis acidity enhancement of triarylboranes

Abstract: The introduction of an o-carborane cage into the triarylborane significantly enhances the Lewis acidity of the boron atom leading to large increase in fluoride ion affinity.

Cited by 107 publications

References 26 publications

Quantum chemical studies on tuning the second-order nonlinear optical molecular switching of triarylborane derivatives

Quantum chemical studies on tuning the second-order nonlinear optical molecular switching of triarylborane derivatives

Synthesis and Fluoride Binding Properties of Tris-pyridinium Borane

Ortho‐Carborane Decorated Multi‐Resonance TADF Emitters: Preserving Local Excited State and High Efficiency in OLEDs

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