Steady-state and transient photolysis of p-nitroaniline in acetonitrile

Ma, Hongjuan; Yao, Shun; Zhang, Jing; Changyong, Pu; Zhao, Sufang; Wang, Min; Xiong, Jie

doi:10.1016/j.jphotochem.2008.11.013

Cited by 8 publications

(5 citation statements)

References 31 publications

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“…The intrinsic spectrum of the component ( Figure S1a Figure S1b in the Supporting Information). This time constant is consistent with the reported lifetime of T 1 PNA (434 ns in ACN [22] and 275 ns in dioxane [30] ).…”

Section: Resultssupporting

confidence: 91%

“…The intrinsic spectrum of the component (Figure S1a in the Supporting Information) is essentially identical to the 0–0.2 μs spectrum (Figure 2 b) and decays with an exponential time constant of 430 ns (Figure S1b in the Supporting Information). This time constant is consistent with the reported lifetime of T 1 PNA (434 ns in ACN22 and 275 ns in dioxane30).…”

Section: Resultssupporting

confidence: 91%

“…The accumulated experimental evidence leads us to the conclusion that the dynamics we have observed (Figure 2 b) is attributed to formation of the triplet state of PNA and its subsequent relaxation back to the ground state. Note that, even in the absence of oxygen, T 1 PNA seems to show self‐quenching effects at higher concentrations of PNA, possibly resulting in the formation of PNA oligomers 22. 30 We did find that at 1 m M , only about 80 % of the excited PNA molecules eventually return to the ground state.…”

Section: Resultsmentioning

confidence: 66%

“…Note that, even in the absence of oxygen, T 1 PNA seems to show self-quenching effects at higher concentrations of PNA, possibly resulting in the formation of PNA oligomers. [22,30] We did find that at 1 mm, only about 80 % of the excited PNA molecules eventually return to the ground state. In contrast, at 0.25 mm, little bleaching signal remains after the decay of T 1 PNA completes.…”

Section: Wwwchemeurjorgmentioning

confidence: 74%

“…p-Nitroaniline is a prototypical push-pull molecule exhibiting a large first hyperpolarizability [5][6][7][8][9][10][11] and nonlinear optical properties with possible applications for electrooptic and second-harmonic generation materials. As a model system, PNA has long been studied both experimentally [4,[12][13][14][15][16][17][18][19][20][21][22] and theoretically. [23][24][25][26][27] A number of ultrafast spectroscopic studies [28][29][30][31] have been done to understand the dynamics of PNA after photoexcitation.…”

Section: Introductionmentioning

confidence: 99%

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Is Our Way of Thinking about Excited States Correct? Time‐Resolved Dispersive IR Study on p‐Nitroaniline

Narra¹,

Chang²,

Witek³

et al. 2012

Chemistry A European J

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Low-lying excited electronic states of an important class of molecules known as push-pull chromophores are central to understanding their potential nonlinear optical properties. Here we report that a combination of high-sensitivity nanosecond time-resolved dispersive IR spectroscopy and DFT calculations on p-nitroaniline (PNA), a prototypical push-pull molecule, reveals that PNA in the lowest excited triplet state has a partial quinoid structure. In this structure, the quinoid configuration is restricted to a part of the phenyl ring adjacent to the NO(2) group. The partial quinoid structure of PNA cannot be explained by a commonly used hybrid of a neutral form and a zwitterionic charge-transfer form. Our findings not only cast doubt on the general applicability of the classical way of looking at excited states, based exclusively on characteristic resonance structures, but also provide deeper insights into excited-state structure of highly polarizable molecular systems.

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Section: Resultssupporting

confidence: 91%

Section: Resultssupporting

confidence: 91%