Advanced Organic Optoelectronic Materials: Harnessing Excited‐State Intramolecular Proton Transfer (ESIPT) Process

Kwon, Ji Eon; Park, Soo Young

doi:10.1002/adma.201102046

Cited by 1,055 publications

(749 citation statements)

References 199 publications

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“…从归一化的荧光光谱可以看出, G1-H 和 G2-H 的荧光强度基本相同, G3-H 略强, G4-H 最低. 根据文献报道 [12,22] , 构象旋转受限不仅是 ESIPT 化合物产生酮式发光的原因, 也是其聚集荧光增强的原因, 因此, 我们推断不同代数树枝形聚合物水溶液荧光强度的差异来源于 ESIPT 基团所受限制作用不同. 各代树枝形聚合物的 PAMAM 骨架大小和发色团数量不同导致形成聚集体的限制性微环境不同, 1 代和 2 代骨架相对较小, 发色团数量较少, 形成的聚集体对构象旋转的限制作用相近, 发色团的发光强度也基本一致; 3 代化合物聚集形成的聚集体结构相比 1～2 代较为紧密, 发色团 …”

Section: 质子化树枝形聚合物 Gn-h 在水中聚集态及光物理研究unclassified

“…激发态分子内质子转移(Excited-State Intramolecular Proton Transfer, ESIPT)化合物具有特殊的激发态光物理过程, 即 ESIPT 化合物在激发态分子内某一基团上的氢核(即质子)能够通过分子内氢键转移到邻近的 N, S, O 等杂原子上, 形成互变异构体, 典型的 ESIPT 化合物有 β-羟基丙稀醛、邻羟基苯甲醛、水杨酸、7-羟基茚酮、羟基黄酮类以及 2-(2'-羟基苯基)苯并唑类等 [12] . 通过基态和激发态间烯醇式(Enol) 图式 1 化合物合成路线和 G3 树枝形聚合物结构式 Scheme 1 Synthetic route of compounds and structure of G3 dendrimer Figure 1 1 H NMR spectra of Model and Gn (400 MHz, DMSO-d 6 )…”

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Synthesis and Photophysical Study of Dendrimers Modified with ESIPT Chromophore

Peng¹,

曾毅²,

陈金平³

et al. 2012

Acta Chim. Sinica

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A series of excited-state intramolecular proton transfer (ESIPT) poly(amido amine) (PAMAM) dendrimers with 4-(benzo [d]thiazol-2-yl)-3-hydroxyphenyl modified at the periphery were synthesized (G0-G4). Functionalization of PAMAM dendrimers was performed through the condensation reaction of dendrimer peripheral amine units and carboxylic groups in DMSO catalyzed by 1-ethyl-3-(3-dimethyllaminopropyl) carbodiimide hydrochloride (EDC). The structures of synthetic compounds G0-G4 were characterized by IR, 1 H NMR, 13 C NMR, and MS. The average functionalization extents of the peripheral amine groups were 99%, 88%, 80%, 83%, and 78% for G0-G4, respectively. The solubility of functionalized dendrimers is dramatically affected by peripheral groups and the dendritic backbone. Model compound dissolves in THF homogeneously, exhibiting enol emission only due to the freely intramolecular rotation and consequently few ESIPT process occurrence. On the contrary, dendrimers form aggregates in THF and present keto emission of ESIPT chromophores, which increases with the dendrimer generation increasing from 0 to 2 and decreases in generation 3 and 4, indicating that the emission of ESIPT chromophores is affected by the PAMAM backbone and peripheral units. From G0 to G2, the increasing congestion of aggregates restrains the intramolecular rotation of ESIPT chromophores, which facilitates the ESIPT process and results in more keto emission. However, a considerable enol emission presents in G3 and G4 because larger dendritic backbone provides more free space and higher polarity microenvironment. The protonated dendrimers, G1-H-G4-H, are soluble in water and form aggregates with a diameter of ca. 20 nm demonstrated by dynamic light scattering experiments. TEM image of aggregates was also obtained revealing vesicle like assemblies. The absorption of ESIPT groups is not affected by protonation of dendritic backbones giving typical absorption of the ESIPT chromophore. The ESIPT chromophore exhibits keto emission exclusively due to the restricted conformation by confined aggregation microenvironments in water, and the emission intensity is slightly affected by dendritic backbones. The lower emission intensity of G4-H can be attributed to the loose microenvironment in the G4-H assembly caused by the larger and flexible dendrimer backbone.

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Section: 质子化树枝形聚合物 Gn-h 在水中聚集态及光物理研究unclassified

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Synthesis and Photophysical Study of Dendrimers Modified with ESIPT Chromophore

Peng¹,

曾毅²,

陈金平³

et al. 2012

Acta Chim. Sinica

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“…However, for many fluo- * Author to whom correspondence should be addressed. E-mail: sqyang@dicp.ac.cn rophores, proton transfer during the excited state is still an effective nonradiative process [3,21]. Over the past few years, many studies have been done by our group to clarify the effects of hydrogen bonding on the excitedstate dynamics of fluorophores, and we have obtained interesting results [22−28].…”

Section: Introductionmentioning

confidence: 99%

Hydrogen Bonding Effects on the Photophysical Properties of 2,3-dihydro-3-keto-1H-pyrido[3,2,1-kl]phenothiazine

Yang

2012

Chinese Journal of Chemical Physics

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Time-dependent density functional theory (TDDFT) and femtosecond transient absorption spectroscopy were used to investigate the photophysical properties of 2,3-dihydro-3-keto-1H-pyrido[3,2,1-kl]phenothiazine (PTZ4) and 3-keto-1H-pyrido[3,2,1-kl]phenothiazine (PTZ5). The calculated results obtained from TDDFT suggest that the red-shifts of the absorption spectra of these two fluorophores in methanol are due to the formation of hydrogen-bonded complexes at the ground state. Four conformers of PTZ4 were obtained by TDDFT. The two fluorescence peaks of PTZ4 in tetrahydrofuran (THF) came from the ICT states of the four conformers. The fluorescence of PTZ4 in THF showed a dependence on the excitation wavelength because of butterfly bending. The excited state dynamics of PTZ4 in THF and methanol were obtained by transient absorption spectroscopy. The lifetime of the excited PTZ4 in methanol was 53.8 ps, and its relaxation from the LE state to the ICT state was completed within several picoseconds. The short lifetime of excited PTZ4 in methanol was due to the formation of out-of-plane model hydrogen bonds between PTZ4 and methanol at the excited state.

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“…It is worth mentioning that the ESIPT process was found to proceed exceptionally fast at a subpicosecond time scale because it involves a negligible activation barrier [16][17][18][19][20][21][22]. This ultrafast nature of ESIPT molecules attracts highest scientific interest whereby paving potential avenues for prospective applications, such as luminescent materials [23,24], fluorescent chemosensors [25], photostabilizers [26,27], molecular probes [28], metal ion sensors [29][30][31], and organic light emitting devices (OLEDs) [32,33].…”

Section: Introductionmentioning

confidence: 99%

TDDFT assessment of excited state intramolecular proton transfer in a panel of chromophore 2-hydroxypyrene-1-carbaldehyde

Shi¹

2016

JAMS

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Abstract. Time dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate excited state intramolecular proton transfer (ESIPT) properties of 2-hydroxypyrene-1-carbaldehyde (HC). Our calculated results of the primary bond lengths and infrared vibrational spectroscopic information show that, upon photoexcitation, the intramolecular hydrogen bond is significantly strengthened in S 1 state, which facilitates the proton transfer process effectively. Furthermore, the electron density distributions of frontier molecular orbitals were demonstrated to be a positive factor for the ESIPT. By the monitor of the characteristic peaks stretching vibration of O-H group in the IR spectra, we have further confirmed the occurrence of ESIPT. The constructed potential energy surface of the S 1 state has also been used to explain the proton transfer process and evaluate the radiationless pathway, indicating that the ESIPT process occurs most easily in HC molecule. PACS: 33.15.Fm

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Advanced Organic Optoelectronic Materials: Harnessing Excited‐State Intramolecular Proton Transfer (ESIPT) Process

Cited by 1,055 publications

References 199 publications

Synthesis and Photophysical Study of Dendrimers Modified with ESIPT Chromophore

Synthesis and Photophysical Study of Dendrimers Modified with ESIPT Chromophore

Hydrogen Bonding Effects on the Photophysical Properties of 2,3-dihydro-3-keto-1H-pyrido[3,2,1-kl]phenothiazine

TDDFT assessment of excited state intramolecular proton transfer in a panel of chromophore 2-hydroxypyrene-1-carbaldehyde

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