scholarly journals Synthesis and Photophysical Properties of a Series of Dimeric Indium Quinolinates

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 34
Author(s):  
Sang Woo Kwak ◽  
Ju Hyun Hong ◽  
Sang Hoon Lee ◽  
Min Kim ◽  
Yongseog Chung ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Nmr Spectroscopy ◽  
1H Nmr Spectroscopy ◽  
Photophysical Properties ◽  
Emission Spectra ◽  
Solvent Polarity ◽  
Low Energy ◽  
Quantum Yields ◽  
Absorption Bands ◽  
Indium Complexes

A novel class of quinolinol-based dimeric indium complexes (1–6) was synthesized and characterized using 1H and 13C(1H) NMR spectroscopy and elemental analysis. Compounds 1–6 exhibited typical low-energy absorption bands assignable to quinolinol-centered π–π* charge transfer (CT) transition. The emission spectra of 1–6 exhibited slight bathochromic shifts with increasing solvent polarity (p-xylene < tetrahydrofuran (THF) < dichloromethane (DCM)). The emission bands also showed a gradual redshift, with an increase in the electron-donating effect of substituents at the C5 position of the quinoline groups. The absolute emission quantum yields (ΦPL) of compounds 1 (11.2% in THF and 17.2% in film) and 4 (17.8% in THF and 36.2% in film) with methyl substituents at the C5 position of the quinoline moieties were higher than those of the indium complexes with other substituents.

scholarly journals Correction: Photophysical properties of the intramolecular excited charge-transfer states of π-expanded styryl phenanthrimidazoles – effect of solvent polarity

RSC Advances ◽  
2016 ◽  
Vol 6 (87) ◽  
pp. 83709-83709
Author(s):  
V. Thanikachalam ◽  
A. Arunpandiyan ◽  
J. Jayabharathi ◽  
P. Ramanathan
Keyword(s):  
Charge Transfer ◽  
Photophysical Properties ◽  
Solvent Polarity ◽  
Effect Of Solvent

Correction for ‘Photophysical properties of the intramolecular excited charge-transfer states of π-expanded styryl phenanthrimidazoles – effect of solvent polarity’ by V. Thanikachalam et al., RSC Adv., 2014, 4, 6790–6806.

Study of the contact charge transfer behavior between cryptophanes (A and E) and fullerene by absorption, fluorescence and 1H NMR spectroscopy

2009 ◽  
Vol 650 (1) ◽  
pp. 118-123 ◽  
Author(s):  
Caihong Zhang ◽  
Weili Shen ◽  
Ruying Fan ◽  
Guomei Zhang ◽  
Lingzhi Shangguan ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Nmr Spectroscopy ◽  
1H Nmr ◽  
1H Nmr Spectroscopy ◽  
Transfer Behavior

scholarly journals The Temperature Dependence of Fundamental Photophysical Properties of [Eu(MeOH-d4)9]3+ Solvates and [Eu.DOTA(MeOH-d4)]- Complexes

2021 ◽  
Author(s):  
Nicolaj Kofod ◽  
Lea Gundorff Nielsen ◽  
Thomas Just Sørensen
Keyword(s):  
Transition Probabilities ◽  
Photophysical Properties ◽  
Transition Probability ◽  
Energy Levels ◽  
Emission Spectra ◽  
Lanthanide Ions ◽  
Quantum Yields ◽  
Luminescence Spectra ◽  
Absorption Cross ◽  
Apparent Lack

The trivalent lanthanide ions show optical transitions between energy levels within the 4f shell. All these transitions are formally forbidden according to the quantum mechanical selection rules used in molecular photophysics. Nevertheless, highly luminescent complexes can be achieved, and terbium(iii) and europium(iii) ions are particularly efficient emitters. This report started when an apparent lack of data in the literature led us to revisit the fundamental photophysics of europium(iii). The photophysical properties of two complexes – [Eu.DOTA(MeOH-d4)]- and [Eu(MeOH-d4)9]3+ – were investigated in deuterated methanol at five different temperatures. Absorption spectra showed decreased absorption cross sections as the temperature was increased. Luminescence spectra and time-resolved emission decay profiles showed a decrease in intensity and lifetime as a temperature was increased. Having corrected the emission spectra for the actual number of absorbed photons and differences in non-radiative pathways, the relative emission probability was revealed. These were found to increase with increasing temperature. The transition probability for luminescence was shown to increase with temperature, while the transition probability for light absorption decreased. The changes in transition probabilities were correlated to a change in the symmetry of the absorber or emitter, with an average increase in symmetry lowering absorption cross section and access to more asymmetric structures increasing the emission rate constant. Determining luminescence quantum yields and the Einstein coefficient for spontaneous emission allowed us to conclude that lowering symmetry increases both. Further, it was found that collisional self-quenching is an issue for lanthanide luminescence, when high concentrations are used. Finally, detailed analysis revealed results that show the so-called ‘Werts’ method’ for calculating radiative lifetimes and intrinsic quantum yields are based on assumption that does not hold for the two systems investigated here. We conclude that we are lacking a good theoretical description of the intraconfigurational f-f transition, and that there are still aspects of fundamental lanthanide photophysics to be explored.<br>

scholarly journals Photophysical Properties of Spirobifluorene-Based o-Carboranyl Compounds Altered by Structurally Rotating the Carborane Cages

Molecules ◽  
2019 ◽  
Vol 24 (22) ◽  
pp. 4135
Author(s):  
Seonah Kim ◽  
Hyunhee So ◽  
Ji Hye Lee ◽  
Hyonseok Hwang ◽  
Hyoshik Kwon ◽  
...  
Keyword(s):  
Radiative Decay ◽  
Photophysical Properties ◽  
High Energy ◽  
Low Energy ◽  
Radiative Decays ◽  
Absorption Bands ◽  
Molecular Features ◽  
Td Dft ◽  
Structural Fluctuations ◽  
Energy Emissions

9,9′-Spirobifluorene-based o-carboranyl compounds C1 and C2 were prepared and fully characterized by multinuclear nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The solid-state structure of C1 was also determined by single-crystal X-ray diffractometry. The two carboranyl compounds display major absorption bands that are assigned to π−π* transitions involving their spirobifluorene groups, as well as weak intramolecular charge-transfer (ICT) transitions between the o-carboranes and their spirobifluorene groups. While C1 only exhibited high-energy emissions (λem = ca. 350 nm) in THF at 298 K due to locally excited (LE) states assignable to π−π* transitions involving the spirobifluorene group alone, a remarkable emission in the low-energy region was observed in the rigid state, such as in THF at 77 K or the film state. Furthermore, C2 displays intense dual emissive patterns in both high- and low-energy regions in all states. Electronic transitions that were calculated by time-dependent-DFT (TD-DFT) for each compound based on ground (S0) and first-excited (S1) state optimized structures clearly verify that the low-energy emissions are due to ICT-based radiative decays. Calculated energy barriers that are based on the relative energies associated with changes in the dihedral angle around the o-carborane cages in C1 and C2 clearly reveal that the o-carborane cage in C1 rotates more freely than that in C2. All of the molecular features indicate that ICT-based radiative decay is only available to the rigid state in the absence of structural fluctuations, in particular the free-rotation of the o-carborane cage.

scholarly journals Effects of Pyrazine Derivatives and Substituted Positions on the Photoelectric Properties and Electromemory Performance of D–A–D Series Compounds

Materials ◽  
2018 ◽  
Vol 11 (10) ◽  
pp. 2063 ◽  
Author(s):  
Xuejing Song ◽  
Lingqian Kong ◽  
Hongmei Du ◽  
Xiangyu Li ◽  
Hanlin Feng ◽  
...  
Keyword(s):  
Flash Memory ◽  
Intramolecular Charge Transfer ◽  
Emission Spectra ◽  
Solvent Polarity ◽  
Band Gap Energy ◽  
Red Shift ◽  
Absorption Bands ◽  
Photoelectric Properties ◽  
Threshold Voltages ◽  
Very High

Pyrazine derivatives quinoxaline and pyridopyrazine were selected as the acceptors, and benzocarbazole was used as the donor to synthesize four different D–A–D compounds. The results showed that 2,3-bis(decyloxy)pyridine[3,4-b]pyrazine (DPP) exhibited stronger electron-withdrawing ability than that of 2,3-bis(decyloxy)quinoxaline (DPx), because DPP possesses one more nitrogen (N) atom, resulting in a red-shift of the intramolecular charge transfer (ICT) absorption bands and fluorescent emission spectra for compounds with DPP as the acceptor compared with those that use DPx as the acceptor. The band-gap energy (Eg) of the four D–A–D compounds were 2.82 eV, 2.70 eV, 2.48 eV, and 2.62 eV, respectively, for BPC-2DPx, BPC-3DPx, BPC-2DPP, and BPC-3DPP. The solvatochromic effect was insignificant when the four compounds were in the ground state, which became significant in an excited state. With increasing solvent polarity, a 30–43 nm red shift was observed in the emissive spectra of the compounds. The thermal decomposition temperatures of the four compounds between 436 and 453 °C had very high thermal stability. Resistor-type memory devices based on BPC-2DPx and BPC-2DPP were fabricated in a simple sandwich configuration, Al/BPC-2DPx/ITO or Al/BPC-2DPP/ITO. The two devices showed a binary non-volatile flash memory, with lower threshold voltages and better repeatability.

Fluorescence of Trans-4-Cyano-4′-dimethylaminostilbene; No Evidence for a TICT State

1983 ◽  
Vol 38 (8) ◽  
pp. 928-936 ◽  
Author(s):  
Henry Gruen ◽  
Helmut Görner
Keyword(s):  
Charge Transfer ◽  
Double Bond ◽  
Relaxation Process ◽  
Singlet State ◽  
Intramolecular Charge Transfer ◽  
Solvent Polarity ◽  
Quantum Yields ◽  
Excited Singlet ◽  
Dual Emission ◽  
Fluorescence Maximum

AbstractThe fluorescence properties of trans-4-cyano-4′-dimethylaminostilbene (trans-1) and a rigid analogue, in which the dimethylaminophenyl group is replaced by an indoline ring, trans-l-(4-cyanophenyl)-2-(5-[2,3-dihydro]N-methylindolyl)ethylene (trans-2) were studied in 20 solvents. The quantum yields of fluorescence (Φf) and of trans→cis photoisomerization (Φt→c) as well as the fluorescence maximum (ν̃f) and the bandwidth (⊿ν̃f) were examined. The activation energies (range: 3.5-7.8 kcal/mol) obtained from <2>f and <£t_c measurements are nearly the same for 1 and 2 in a given solvent. Φf , ν̃f and ⊿ν̃f as a function of solvent polarity and temperature show similar trends for 1 and 2. No dual emission was observed for either of the cyanostilbenes. These findings indicate that a twisted intramolecular charge transfer (TICT) state is not involved in the relaxation process of the first excited trans singlet state (1t*). The main deactivation pathway of 1t* competing with fluorescence is trans→cis photoisomerization by twisting about the C = C double bond in the first excited singlet state for both.

scholarly journals Hydrogen bonding in push-pull 5-substituted-2-alkylidene-4-oxothiazolidines: 1H-MNR spectroscopic study

2003 ◽  
Vol 68 (1) ◽  
pp. 1-7 ◽  
Author(s):  
R. Markovic ◽  
A. Shirazi ◽  
Zdravko Dzambaski ◽  
Marija Baranac ◽  
Dragica Minic-Popovic
Keyword(s):  
Hydrogen Bonding ◽  
Nmr Spectroscopy ◽  
Hydrogen Bonds ◽  
Spectroscopic Study ◽  
1H Nmr ◽  
1H Nmr Spectroscopy ◽  
Solvent Polarity ◽  
Concentration Effect ◽  
Intermolecular Hydrogen Bonding ◽  
Dynamic 1H Nmr

Application of dynamic 1H-NMR spectroscopy added to the understanding of the hydrogen bonds existing in the structurally related 5-substituted-2-alkylidene-4-oxothiazolidines in polar and apolar solvents. The equilibrated mixtures of these typical push-pull alkenes in CDCl3 consist of the intramolecularly H-bonded (E)-isomer and intermolecularly H-bonded (Z)-isomer in varying proportions which depend on the solvent polarity. For the representative of the series (Z)-2-(5-ethoxycarbonylmethyl-4-oxothiazolidin-2-ylidene)-1-phenylethanone a concentration effect on the degree of intermolecular hydrogen bonding in apolar CDCl3 has been studied.

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.

The electronic spectra of nickel(II) bis(dithiocarbamate) chelates

1980 ◽  
Vol 45 (3) ◽  
pp. 791-799 ◽  
Author(s):  
Drahomír Oktavec ◽  
Bohumil Síleš ◽  
Jozef Štefanec ◽  
Elena Korgová ◽  
Ján Garaj
Keyword(s):  
Charge Transfer ◽  
Nitrogen Atom ◽  
Electronic Spectra ◽  
Alkyl Chain ◽  
Solvent Polarity ◽  
Blue Shift ◽  
Red Shift ◽  
Band Intensity ◽  
Absorption Bands

The synthesis and electronic spectra of the chelates of nickel(II) dithiocarbamates with ligands derived from dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, diisopropyl-, methylisopropylamine, piperidine, morpholine and piperazine are discussed. The absorption bands in the chelate spectra around 220 and 245 nm are assigned to absorption localized primarily in the S-C=S and N-C=S ligand groups. The analytically most important band with λmax around 330 nm assigned to M-L charge transfer is affected by alkyl substituents on the nitrogen atom and by the solvent polarity. The lengthening of the alkyl chain causes the increase in the intensity of the band and red-shift of its λmax; the increase of the polarity of the solvent leads to an increase in the band intensity and a blue shift.

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