ChemInform Abstract: Luminescence and Charge Transfer. Part 3. The Use of Chromophores with ICT (Internal Charge Transfer) Excited States in the Construction of Fluorescent PET (Photoinduced Electron Transfer) pH Sensors and Related Absorption pH Sensors

ChemInform ◽  
2010 ◽  
Vol 24 (51) ◽  
pp. no-no
Author(s):  
A. P. DE SILVA ◽  
H. Q. N. GUNARATNE ◽  
P. L. M. LYNCH ◽  
A. J. PATTY ◽  
G. L. SPENCE
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Excited States ◽  
Photoinduced Electron Transfer ◽  
Ph Sensors ◽  
Internal Charge Transfer ◽  
Internal Charge

1,3,5-Triarylpyrazolines — pH-driven off-on-off molecular logic devices based on a “receptor1-fluorophore-spacer-receptor2” format with internal charge transfer (ICT) and photoinduced electron transfer (PET) mechanisms

2015 ◽  
Vol 93 (2) ◽  
pp. 199-206 ◽  
Author(s):  
Ramon Zammit ◽  
Maria Pappova ◽  
Esther Zammit ◽  
John Gabarretta ◽  
David C. Magri
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Charge Transfer ◽  
Photoinduced Electron Transfer ◽  
Photophysical Properties ◽  
Molecular Probes ◽  
Quantum Yields ◽  
Ph Sensing ◽  
Internal Charge Transfer ◽  
Internal Charge

The excited state photophysical properties of the 1,3,5-triarylpyrazolines 1–4 were studied in methanol and 1:1 (v/v) methanol–water, as well as 1:4 (v/v) methanol–water and water by fluorescence spectroscopy. The molecules 2–4 incorporate a “receptor1-fluorophore-spacer-receptor2” format while 1 is a reference compound based on a “fluorophore-receptor1” design. The molecular probes operate according to photoinduced electron transfer (PET) and internal charge transfer (ICT) processes. At basic and neutral pHs, 2–4 are essentially nonfluorescent due to PET from the electron-donating dimethylamino moiety appended on the 5-phenyl ring to the excited state of the 1,3,5-triarylpyrazoline fluorophore. At proton concentrations of 10−3 mol/L, the dimethylamino unit is protonated resulting in a strong blue fluorescence about 460 nm with significant quantum yields up to 0.54. At acid concentrations above 10−2 mol/L, fluorescence quenching is observed by an ICT mechanism due to protonation of the pyrazoline chromophore. Symmetrical off-on-off fluorescence–pH profiles are observed, spanning six log units with a narrow on window within three pH units. Hence, 2–4 are novel examples of ternary photonic pH sensing molecular devices.

scholarly journals Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers

2020 ◽  
Vol 11 (36) ◽  
pp. 9962-9970 ◽  
Author(s):  
Shaoyang Wang ◽  
Alexandra D. Easley ◽  
Ratul M. Thakur ◽  
Ting Ma ◽  
Junyeong Yun ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Internal Electron ◽  
Internal Charge Transfer ◽  
Internal Charge

Conjugated radical polymers can exhibit internal electron transfer depending on the radical loading.

Substituent Effects on Twisted Internal Charge Transfer Excited States of N-Borylated Carbazoles and (Diphenylamino)boranes

2012 ◽  
Vol 116 (4) ◽  
pp. 1151-1158 ◽  
Author(s):  
Jian Wang ◽  
Ying Wang ◽  
Takuhiro Taniguchi ◽  
Shigehiro Yamaguchi ◽  
Stephan Irle
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Substituent Effects ◽  
Internal Charge Transfer ◽  
Internal Charge

Charge transfer emissive singlet excited states and photoinduced electron transfer properties in the diarylideneacetone compounds (RCHCH)2CO; R = phenyl, 1- and 2-naphthyl, 3-(N-ethylcarbazoyl), and 4-(C5H5)Fe(C5H4C6H4CHCH(CO)CHCHC6H5)

1990 ◽  
Vol 68 (12) ◽  
pp. 2278-2288 ◽  
Author(s):  
Pierre D. Harvey ◽  
Liangbing Gan ◽  
Christiane Aubry
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Charge Transfer ◽  
Excited States ◽  
Photoinduced Electron Transfer ◽  
Flash Photolysis ◽  
Reduction Process ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Electron Reduction

Four diarylideneacetone compounds ((RCHCH)2CO, where the aryl groups are phenyl (dba), 1-naphthyl (1-dNapha), 2-naphthyl (2-dNapha), and 3-(N-ethylcarbazoyl) (dNECa)), and 4-(C5H5)Fe(C5H4C6H4CHCH(CO)CHCH(C6H5) (dba-Fc) have been prepared and characterized. The compounds are found to be fluorescent and photochemically and reversibly electrochemically active. The lowest-energy absorption bands for the diarylideneacetones are assigned to a charge transfer (CT) electronic transition, except for dba-Fc, in which a ferrocenyl ligand field transition assignment is made. The 77 K CT absorption and fluorescence bands are vibrationally structured (vibrational spacings = 1260–1360 cm−1). While the fluorescence decay at 293 K is monoexponential, the excited state fluorescence lifetimes (τF) for the 77 K samples exhibit double exponential decays, the short component being 0.38–0.64 ns and the long one 3.5–10.9 ns. The photophysical results are interpreted in terms of excited state deactivation processes dominated by radiationless pathways that are associated with the presence of fluorescent species with different geometries. Only the dNECa compound is found to be fluorescent in solution at 298 K [Formula: see text]. Cyclic voltammetry and coulometry measurements suggest that a reversible one-electron reduction process and an irreversible higher potential one-electron reduction process take place in the −1 to −2 V vs. SSCE range. In addition, dba-Fc also exhibits an electrochemically reversible one-electron oxidation wave at 0.52 V vs. SSCE centered at the ferrocenyl group. These results together with the spectroscopic electronic data have permitted evaluation of the reduction potentials of the lowest singlet (CT excited states (E1−/*);they range from 1.4 to 2.2 V vs. SSCE, with dba being the strongest photooxidizing agent and dNECa the weakest. Photoinduced intermolecular electron transfer reactions have been investigated by steady state fluorescence techniques and picosecond flash photolysis spectroscopy for dNECa and dba, respectively. The bimolecular deactivation rate constants, kq, for the reductive photoinduced electron transfer reactions of dNECa with diphenylamine (DPA) (kq = (2.65 ± 0.25) × 107 M−1 s−1) and N, N, N′, N′-tetramethylphenylenediamine (TMPM) (kq = (1.38 ± 0.03) × 108 M−1 s−1) have been obtained in THF solutions at 293 K. No fluorescence quenching is observed when oxidative and energy transfer quenchers are used with dNECa. For the non-emissive dba compound at room temperature, picosecond flash photolysis experiments show that quenching of the broad dba transient band (~500 nm) does indeed occur between 5 and 10 ns. Keywords: dibenzylideneacetone, charge transfer, photoelectron transfer.

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