Photoswitching of Redox Potentials and Spectroscopic Properties in the UV/vis Region

2005 ◽  
Vol 60 (1) ◽  
pp. 75-82 ◽  
Author(s):  
Nedko Drebov ◽  
Nikolai Tyutyulkov ◽  
Stojan Karabunarliev ◽  
Fritz Dietz
Keyword(s):  
Spectroscopic Properties ◽  
Visible Spectral Region ◽  
Redox Potentials ◽  
Electron Systems ◽  
Excitation Energies ◽  
Reduction Potentials ◽  
Open Ring ◽  
Wavelength Absorption ◽  
Donor Acceptor ◽  
Ct Transitions

The photoswitching of optical and electrochemical properties of di-donor, di-acceptor and donor-acceptor substituted photochromic tetrahydropyrene - [2,2]metacyclophanene and dihydropyrene - [2,2]metacyclophanediene systems has been studied theoretically. A switching of the halfwave oxidation and reduction potentials should be possible in the case of bis(pyridinium) and bis(hydroxyphenyl) substituted systems. Because of the relatively great perturbation of the planarity of the π-electron systems by large torsion of the substituents out of the π-electron structure of the photochromic system and the stair-like structure of the ring-opened isomer, relatively large excitation energies for CT transitions have been calculated with the AM1-CI procedure. The ring-closed structures should absorb in the visible spectral region, and the open-ring isomers should have a longest-wavelength absorption in the UV region.

scholarly journals Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides

2021 ◽  
Author(s):  
Jinhui Xu ◽  
Jilei Cao ◽  
Xiangyang Wu ◽  
Han Wang ◽  
Xiaona Yang ◽  
...  
Keyword(s):  
Limited Range ◽  
Redox Potentials ◽  
Aryl Chlorides ◽  
Aryl Radicals ◽  
Reduction Potentials ◽  
Anion Form ◽  
Donor Acceptor ◽  
High Reduction ◽  
Very High ◽  
Excited Radical

Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis, and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 V to +1.79 V. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN<sup>•</sup><sup>−</sup>*, which can be used to activate reductively recalcitrant aryl chlorides (E<sub>red </sub>≈ -1.9 to -2.9 V) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes, respectively.

scholarly journals Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides

2021 ◽  
Author(s):  
Jinhui Xu ◽  
Jilei Cao ◽  
Xiangyang Wu ◽  
Han Wang ◽  
Xiaona Yang ◽  
...  
Keyword(s):  
Limited Range ◽  
Redox Potentials ◽  
Aryl Chlorides ◽  
Aryl Radicals ◽  
Reduction Potentials ◽  
Anion Form ◽  
Donor Acceptor ◽  
High Reduction ◽  
Very High ◽  
Excited Radical

Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis, and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 V to +1.79 V. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN<sup>•</sup><sup>−</sup>*, which can be used to activate reductively recalcitrant aryl chlorides (E<sub>red </sub>≈ -1.9 to -2.9 V) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes, respectively.

scholarly journals Photophysics and Electrochemistry of Biomimetic Pyranoflavyliums: What Can Bioinspiration from Red Wines Offer?

Photochem ◽  
2022 ◽  
Vol 2 (1) ◽  
pp. 9-31
Author(s):  
Eli Misael Espinoza ◽  
John Anthony Clark ◽  
Mimi Karen Billones ◽  
Gustavo Thalmer de Medeiros Silva ◽  
Cassio Pacheco da Silva ◽  
...  
Keyword(s):  
Dye Sensitized Solar Cells ◽  
Spectroscopic Properties ◽  
Visible Spectral Region ◽  
Synthetic Dyes ◽  
Red Wines ◽  
Reduction Potentials ◽  
Ability To Act ◽  
Energy Science ◽  
P Type ◽  
Sensitized Solar Cells

Natural dyes and pigments offer incomparable diversity of structures and functionalities, making them an excellent source of inspiration for the design and development of synthetic chromophores with a myriad of emerging properties. Formed during maturation of red wines, pyranoanthocyanins are electron-deficient cationic pyranoflavylium dyes with broad absorption in the visible spectral region and pronounced chemical and photostability. Herein, we survey the optical and electrochemical properties of synthetic pyranoflavylium dyes functionalized with different electron-donating and electron-withdrawing groups, which vary their reduction potentials over a range of about 400 mV. Despite their highly electron-deficient cores, the exploration of pyranoflavyliums as photosensitizers has been limited to the “classical” n-type dye-sensitized solar cells (DSSCs) where they act as electron donors. In light of their electrochemical and spectroscopic properties, however, these biomimetic synthetic dyes should prove to be immensely beneficial as chromophores in p-type DSSCs, where their ability to act as photooxidants, along with their pronounced photostability, can benefit key advances in solar-energy science and engineering.

Correlation of the photoelectron and electronic spectra of thiochromones and thiochromanones with their electrochemical data

1979 ◽  
Vol 57 (6) ◽  
pp. 638-644 ◽  
Author(s):  
Rafik O. Loutfy ◽  
Ian W. J. Still ◽  
Michael Thompson ◽  
Toong S. Leong
Keyword(s):  
Gas Phase ◽  
Substituent Effects ◽  
Spectroscopic Properties ◽  
Oxidation Potential ◽  
Molecular Orbitals ◽  
Absolute Difference ◽  
Linear Free Energy Relationship ◽  
Redox Potentials ◽  
Reduction Potentials ◽  
Oxidation Potentials

The gas phase ionization potentials, electrochemical redox potentials and spectroscopic properties of a series of thiochroman-4-one and thiochromone derivatives have been studied. A dramatic shift in the energies of the lowest vacant and highest occupied molecular orbitals of the parent thiochromanone as a function of the addition of a double bond and/or oxidation of the sulphur atom was observed. This shift in energy of the molecular orbitals was reflected in their spectroscopic characteristics. The lowest singlet (and triplet) state of compounds 1–3 in solution is π,π* in nature, while that of compounds 4–6 is n,π*. These results are best explained in terms of substituent effects on the energetics of the acetophenone moiety. The change in the nature of the lowest excited state from π,π* (1–3) to n,π* (4–6) should result in quite different types of photochemistry for the two series.A linear free-energy relationship between the singlet and triplet energies and the absolute difference between the oxidation and reduction potentials of the two series was found. These correlations have been utilized to estimate the half-wave oxidation potentials of compounds 3–6. A correlation was found to exist between the gas phase ionization potential and the solution electrochemical oxidation potential.

Systematic calculations of energy levels and transitions rates in Mo XXVIII

2020 ◽  
Vol 75 (8) ◽  
pp. 739-747
Author(s):  
Feng Hu ◽  
Yan Sun ◽  
Maofei Mei
Keyword(s):  
Energy Levels ◽  
Oscillator Strengths ◽  
Atomic Data ◽  
Data Sets ◽  
Electron Systems ◽  
Excitation Energies ◽  
Experimental Values ◽  
Qed Effects ◽  
Hyperfine Structures ◽  
Good Agreement

AbstractComplete and consistent atomic data, including excitation energies, lifetimes, wavelengths, hyperfine structures, Landé gJ-factors and E1, E2, M1, and M2 line strengths, oscillator strengths, transitions rates are reported for the low-lying 41 levels of Mo XXVIII, belonging to the n = 3 states (1s22s22p6)3s23p3, 3s3p4, and 3s23p23d. High-accuracy calculations have been performed as benchmarks in the request for accurate treatments of relativity, electron correlation, and quantum electrodynamic (QED) effects in multi-valence-electron systems. Comparisons are made between the present two data sets, as well as with the experimental results and the experimentally compiled energy values of the National Institute for Standards and Technology wherever available. The calculated values including core-valence correction are found to be in a good agreement with other theoretical and experimental values. The present results are accurate enough for identification and deblending of emission lines involving the n = 3 levels, and are also useful for modeling and diagnosing plasmas.

scholarly journals Optical Activation Behavior of Ion Implanted Acceptor Species in GaN

2000 ◽  
Vol 5 (S1) ◽  
pp. 507-513 ◽  
Author(s):  
B.J. Skromme ◽  
G.L. Martinez
Keyword(s):  
Variable Temperature ◽  
Spectroscopic Properties ◽  
Acceptor Pair ◽  
High Quality ◽  
Shallow Acceptor ◽  
Implantation Damage ◽  
Donor Acceptor ◽  
Optical Activation ◽  
Optical Binding ◽  
Dose Dependent

Ion implantation is used to investigate the spectroscopic properties of Mg, Be, and C acceptors in GaN. Activation of these species is studied using low temperature photoluminescence (PL). Low dose implants into high quality undoped hydride vapor phase epitaxial (HVPE) material are used in conjunction with high temperature (1300 °C) rapid thermal anneals to obtain high quality spectra. Dramatic, dose-dependent evidence of Mg acceptor activation is observed without any co-implants, including a strong, sharp neutral Mg acceptor-bound exciton and strong donor-acceptor pair peaks. Variable temperature measurements reveal a band-to-acceptor transition, whose energy yields an optical binding energy of 224 meV. Be and C implants yield only slight evidence of shallow acceptor-related features and produce dose-correlated 2.2 eV PL, attributed to residual implantation damage. Their poor optical activation is tentatively attributed to insufficient vacancy production by these lighter ions. Clear evidence is obtained for donor-Zn acceptor pair and acceptor-bound exciton peaks in Zn-doped HVPE material.

Synthesis and hydrolysis of gas-phase lanthanide and actinide oxide nitrate complexes: a correspondence to trivalent metal ion redox potentials and ionization energies

2015 ◽  
Vol 17 (15) ◽  
pp. 9942-9950 ◽  
Author(s):  
Ana F. Lucena ◽  
Célia Lourenço ◽  
Maria C. Michelini ◽  
Philip X. Rutkowski ◽  
José M. Carretas ◽  
...  
Keyword(s):  
Gas Phase ◽  
Metal Ion ◽  
Oxidation States ◽  
Redox Potentials ◽  
Trivalent Metal ◽  
Ionization Energies ◽  
Reduction Potentials ◽  
Hydrolysis Of ◽  
Nitrate Complexes

Gas-phase hydrolysis of lanthanide/actinide MO3(NO3)3−ions relates to the stabilities of the MIVoxidation states, which correlate with IV/III solution reduction potentials and 4th ionization energies.

scholarly journals Substitution Effect on the Charge Transfer Processes in Organo-Imido Lindqvist-Polyoxomolybdate

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 44 ◽  
Author(s):  
Patricio Hermosilla-Ibáñez ◽  
Kerry Wrighton-Araneda ◽  
Walter Cañón-Mancisidor ◽  
Marlen Gutiérrez-Cutiño ◽  
Verónica Paredes-García ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Theoretical Study ◽  
Bathochromic Shift ◽  
Substitution Effect ◽  
Spectroscopic Properties ◽  
Electrochemical Studies ◽  
Redox Potentials ◽  
Metal Centre ◽  
Transfer Processes ◽  
Organic Fragment

Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu4N]2[Mo6O18NC6H4N3C2H2]) (1) and a highly conjugated fluorene ([n-Bu4N]2[Mo6O18NC13H9]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.

scholarly journals Porphyrinoid–Fullerene Hybrids as Candidates in Artificial Photosynthetic Schemes

2019 ◽  
Vol 5 (3) ◽  
pp. 57 ◽  
Author(s):  
Vasilis Nikolaou ◽  
Asterios Charisiadis ◽  
Christina Stangel ◽  
Georgios Charalambidis ◽  
Athanassios G. Coutsolelos
Keyword(s):  
Scientific Community ◽  
Light Harvesting ◽  
Reorganization Energy ◽  
Photosynthetic Reaction Center ◽  
Comprehensive Analysis ◽  
The Novel ◽  
Reduction Potentials ◽  
Donor Acceptor ◽  
Artificial Photosynthetic ◽  
Natural Photosynthesis

Natural photosynthesis inspired the scientific community to design and synthesize molecular assemblies that possess advanced light-harvesting and electron-transfer features. In this review, we present the preparation and the photophysical investigation of novel porphyrin–fullerene hybrids acting as artificial photosynthetic systems. Porphyrinoids stand as chlorophyll analogues and have emerged as suitable photosensitizers in supramolecular electron donor–acceptor hybrids. Fullerenes (C60) are versatile electron acceptors with small reorganization energy and low reduction potentials. The novel derivatives presented herein mimic the fundamental features of the photosynthetic reaction center, namely, light harvesting, charge separation, and charge transport. To this end, a comprehensive analysis on these key processes that occur in various porphyrin–fullerene entities is illustrated in this work.

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