Stable Oxindolyl‐Based Analogues of Chichibabin's and Müller's Hydrocarbons

Wang, Jian; Xu, Xingdong; Phan, Hoa; Herng, Tun Seng; Gopalakrishna, Tullimilli Y.; Li, Guangwu; Ding, Jun; Wu, Jishan

doi:10.1002/ange.201708612

Cited by 13 publications

(3 citation statements)

References 32 publications

(15 reference statements)

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“…This indicates that this site should be a prime target for substitution with bromine or chlorine atoms: substitution would decrease the hyperfine contribution and hinder the mesithyl rotation. This result also confirms the previous assignments on different p-delocalized paramagnetic structures with unresolved electron spin dipolar interactions, [26][27][28][29][30]34,[66][67][68][69] and is consistent with the previous observation of dipolar coupling solely in small radicaloids. 19,35 Trends reported for linear acenes show that the value of the dipolar coupling strongly decreases when increasing the length of the molecule, 70,71 and this agrees perfectly with our observations and the lack of a half-field line.…”

Section: Theoretical Modelingsupporting

confidence: 93%

Synthetic tuning of the quantum properties of open-shell radicaloids

Lombardi

Alexandropoulos

et al. 2021

Chem

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Section: Theoretical Modelingsupporting

confidence: 93%

Synthetic tuning of the quantum properties of open-shell radicaloids

Lombardi

Alexandropoulos

et al. 2021

Chem

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“…Electronic Structure and Fluorescent Property of Dimers. As is well known that free radical molecules are generally unstable, 31 two free radicals tend to form a dimer by the central head-to-head C−C bond to attenuate reactivity. 32,33 Thus, we investigated the dimers composed of both the title molecules.…”

Section: Resultsmentioning

confidence: 99%

“…As is well known that free radical molecules are generally unstable, two free radicals tend to form a dimer by the central head-to-head C–C bond to attenuate reactivity. , Thus, we investigated the dimers composed of both the title molecules. To obtain the stable geometry of the dimer of TTM-3NCz and TTM-3PCz, the relaxing potential energy scan was performed at the UB3LYP/6-31+G(d) level for each dimer.…”

Section: Resultsmentioning

confidence: 99%

Innovative Organic Electroluminescent Materials with a Doublet Ground State: A Theoretical Investigation

Zhu

2020

J. Phys. Chem. A

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The displaced and distorted harmonic oscillator model, which has been proven to be appropriate in calculating vibronic spectra, is employed to treat the emission spectrum of title molecules in combination with a thermal vibration correlation function. The calculated results indicate that the main peak of the emission spectrum is visibly impacted by the normal modes with lower frequencies and that the shoulder peak is originated from the middle-frequency modes. On the level of time-dependent density functional theory (TDDFT), the calculated fluorescence lifetimes of TTM-3NCz and TTM-3PCz are 22.1 and 26.0 ns, respectively, which happen to coincide with the observed values of TTM-3NCz (17.2 ns) and TTM-3PCz (21.2 ns). The above data indicate that both the calculated radiative decay rates are reasonable at room temperature. Furthermore, we investigate the influence of the Duschinsky effect on the fluorescence quantum efficiency (FQE). When it is considered, the predicted FQE of the TTM-3NCz molecule is only 0.11%, and the observed value (49% in toluene) deviates significantly. If we ignore the Duschinsky effect, the FQE of TTM-3NCz increases dramatically to 41.8%. For the TTM-3PCz molecule (the FQE is 46% in toluene), the calculated FQE is 0.042% with the Duschinsky effect and increases to 45.2% without the Duschinsky effect. This phenomenon might be related to external factors and the nature of the TDDFT only considering a single configuration. In addition, the fluorescent properties of the fluorinated TTM-3NCz molecules are studied predictably. The obtained results show that the perfluorinated TTM-3NCz shows better luminous performance due to larger oscillator strength. Finally, the dimers, which are composed of both single title molecules, are explored theoretically to determine how they impact the fluorescent property; however, the effect can be nearly eliminated because of the small binding energies.

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N‐Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons

Rottschäfer

Neumann

et al. 2018

Angewandte Chemie

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Stable N-heterocyclic carbene analogues of Thiele and Chichibabin hydrocarbons,[ (IPr)(C 6 H 4 )(IPr)] and [(IPr)(C 6 H 4 ) 2 (IPr)] (4 and 5,r espectively;I Pr = C{N(2,6-iPr 2 C 6 H 3 )} 2 CHCH), are reported. In anickel-catalyzed double carbenylation of 1,4-Br 2 C 6 H 4 and 4,4'-Br 2 (C 6 H 4 ) 2 with IPr (1), [(IPr)(C 6 H 4 )(IPr)](Br) 2 (2)a nd [(IPr)(C 6 H 4 ) 2 (IPr)](Br) 2 (3) were generated, whichr espectively afforded 4 and 5 as crystalline solids upon reduction with KC 8 .E xperimental and computational studies support the semiquinoidal nature of 5 with as mall singletÀtriplet energy gap DE SÀT of 10.7 kcal mol À1 ,w hereas 4 features more quinoidal character with ar ather large DE SÀT of 25.6 kcal mol À1 .I nv iew of the low DE SÀT , 4 and 5 may be described as biradicaloids.Moreover, 5 has considerable (41 %) diradical character.

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Stable Oxindolyl‐Based Analogues of Chichibabin's and Müller's Hydrocarbons

Cited by 13 publications

References 32 publications

Synthetic tuning of the quantum properties of open-shell radicaloids

Synthetic tuning of the quantum properties of open-shell radicaloids

Innovative Organic Electroluminescent Materials with a Doublet Ground State: A Theoretical Investigation

N‐Heterocyclic Carbene Analogues of Thiele and Chichibabin Hydrocarbons

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