Excited-State Intramolecular Proton Transfer via a Preexisting Hydrogen Bond in Semirigid Polyquinoline

Chang, Dong Wook; Kim, Sehoon; Park, Soo Young; Yu, Hyunung; Jang, Du‐Jeon

doi:10.1021/ma000126g

Cited by 37 publications

(44 citation statements)

References 20 publications

(27 reference statements)

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“…We examined the possibility of ESIPT in this designed chromophore with semiempirical molecular orbital calculation (PM3 parameter, Mopac 97). 4 In all the optimized geometries in four levels of the photocycle, quinoline and phenolic group, which form cyclic intramolecular H bond, were found to be almost in-plane. Based on the reaction path obtained from the calculated energies and bond lengths of normal enol form (N), tautomeric keto form (T), and transition state (TS) in the ground and the first excited singlet states, ESIPT was found to be quite probable energetically.…”

Section: Theoretical Design Of Esipt Chromophorementioning

confidence: 91%

“…Very recently, we reported highly concentrated but still ESIPT-active solid media, i.e., films of a semi-rigid polyquinoline and poly(aryl ether) dendrimers possessing a novel photo-tautomerizable quinoline as a repeating unit and core, respectively. [4][5][6][7] Here we describe the recent progress, i.e., theoretical design of a quinoline-based ESIPT chromophore and its optical properties in polymeric and dendritic systems including stimulated emission and amplified spontaneous emission.…”

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confidence: 99%

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Molecular photonics materials with excited-state intramolecular proton transfer (ESIPT) activity

Park

Kim

2003

SPIE Proceedings

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Synthesis and properties of novel excited-state intramolecular proton transfer (ESIPT) materials recently developed in our group are described. Highly efficient ESIPT in polymeric system has been investigated theoretically and experimentally with a semi-rigid polyquinoline (PQH, PQDH) possessing an intramolecular tautomerizable hydrogen bond. Poly(aryl ether) dendrimers of three different generations that are cored with photo-tautomerizable quinoline (QGn, n=1,2,3) were also synthesized and characterized to investigate the effect of dendritic architecture on the ESIPT activity. Stimulated emission and amplified spontaneous emission in these organic materials system are discussed in terms of ESIPT activity.

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Section: Theoretical Design Of Esipt Chromophorementioning

confidence: 91%

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confidence: 99%

Molecular photonics materials with excited-state intramolecular proton transfer (ESIPT) activity

Park

Kim

2003

SPIE Proceedings

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“…It is believed that the alkyl radicals are the primary initiating species in this reaction. The following borate salts were reported as being useful in visible light 125 Another complex that was also found to be useful in visible light for free radical initiation is 133,134 : 125 Tetraarylborate salts by themselves were thought to be inefficient, because radicals that result from their decomposition are less stable and also more difficult to generate from oxidized borates .…”

Section: Light-associated Reactions Of Synthetic Polymers 2 Photosenmentioning

confidence: 99%

“…133 Chang et al, 134 noted from the literature that the excited-state intramolecular proton transfer is a form of phototautomerization occurring in the excited states of the molecules possessing cyclic intramolecular or solventbridged hydrogen bonds. 133 Chang et al, 134 noted from the literature that the excited-state intramolecular proton transfer is a form of phototautomerization occurring in the excited states of the molecules possessing cyclic intramolecular or solventbridged hydrogen bonds.…”

Section: Light-associated Reactions Of Synthetic Polymersmentioning

confidence: 99%

Light-Associated Reactions of Synthetic Polymers

Ravve¹

2006

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“…Only a few investigations on the ESIPT of large molecules were reported in experimental investigation. [26][27][28] For instance, Yang et al 26 observed the aggregationinduced ESIPT emission enhancement of some large molecules, and Park et al 27,28 demonstrated that a few dendric polyether molecules were able to undergo ESIPT emission as photoexcitation. Experimental and theoretical investigation on the occurrence of ESIPT of large molecules becomes very necessary.…”

Section: Introductionmentioning

confidence: 99%

Excited State Intramolecular Proton Transfer of New Diphenyl‐ ethylene Derivatives Bearing Imino Group: A Combination of Experimental and Theoretical Investigation

et al. 2010

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In this paper, we described the synthesis and characterization of new diphenylethylene bearing imino group. We concentrated particularly on the investigation of the possibility of the excited state intramolecular charge transfer (ESIPT) of the new dyes experimentally and theoretically. The absorption and fluorescence spectroscopy of the dyes were determined in various solvents. The results showed that the maximal absorption wavelength of 2-[(4'-N,N-dimethylamino-diphenylethylene-4-ylimino)methyl]phenol (C1) and 4-[(4'-N,N-dimethylamino-diphenylethylene-4-ylimino)methyl]phenol (C2) exhibited almost independence on the solvent polarity. While as contrast, the maximal fluorescence wavelength of the dyes showed somewhat dependence on the solvent polarity. In particular, C1 displayed well-separated dual fluorescence spectroscopy. The second fluorescence peak was characterized with an "abnormal" fluorescence emission wavelength in aprotic solvents with large Stokes shift (ca. 140 nm in THF), which was much more than normal Stokes shift (ca. 30 nm in THF). This emission spectroscopy could be assigned to ESIPT emission. On the other hand, the ESIPT fluorescence of C1 was much reduced or lost in the protic solvents. While, only normal fluorescence emission was detected in various solvents. Although the absorption maxima of C1 exhibited about 10 nm red-shift with respect to those of C2, the normal fluorescence maxima of C1 and C2 were almost identical in various solvents. These results suggested that C1 could undergo ESIPT, but C2 was not able to proceed ESIPT. The molecular geometry optimization of phototautomers in the ground electronic state (S 0 ) was carried out with HF method (Hartree-Fock) and at DFT level (Density Functional Theory) using B3LYP both, while the CIS was employed to optimize the geometries of the first singlet excited state (S 1 ) of the phototautomers of C1 and C2 respectively. The properties of the ground state and the excited state of the phototautomers of C1 and C2, including the geometrical parameter, the energy, the frontier orbits, the Mulliken charge and the dipole moment change were performed and compared completely. The data were analyzed further based on our experimental results. Furthermore, the absorption and fluorescence spectra were calculated in theory and compared with the measured ones. The rate constant of internal proton transfer (9.831×10 11 s -1 ) of C1 was much lower than that of salicylidene methylamine (C3, 2.045×10 15 s -1 ), which was a typical Schiff base compound and was well demonstrated to undergo ESIPT easily under photoexcitation.

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Excited-State Intramolecular Proton Transfer via a Preexisting Hydrogen Bond in Semirigid Polyquinoline

Cited by 37 publications

References 20 publications

Molecular photonics materials with excited-state intramolecular proton transfer (ESIPT) activity

Molecular photonics materials with excited-state intramolecular proton transfer (ESIPT) activity

Light-Associated Reactions of Synthetic Polymers

Excited State Intramolecular Proton Transfer of New Diphenyl‐ ethylene Derivatives Bearing Imino Group: A Combination of Experimental and Theoretical Investigation

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