Excited States of Nitro-Polypyridine Metal Complexes and Their Ultrafast Decay. Time-Resolved IR Absorption, Spectroelectrochemistry, and TD-DFT Calculations offac-[Re(Cl)(CO)3(5-Nitro-1,10-phenanthroline)]

2005 ◽  
Vol 109 (28) ◽  
pp. 6147-6153 ◽  
Author(s):  
Anders Gabrielsson ◽  
Pavel Matousek ◽  
Michael Towrie ◽  
František Hartl ◽  
Stanislav Záliš ◽  
...  
2020 ◽  
Author(s):  
Masaki Saigo ◽  
Kiyoshi Miyata ◽  
Hajime Nakanotani ◽  
Chihaya Adachi ◽  
Ken Onda

We have investigated the solvent-dependence of structural changes along with intersystem crossing of a thermally activated delayed fluorescence (TADF) molecule, 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (o-3CzBN), in toluene, tetrahydrofuran, and acetonitrile solutions using time-resolved infrared (TR-IR) spectroscopy and DFT calculations. We found that the geometries of the S1 and T1 states are very similar in all solvents though the photophysical properties mostly depend on the solvent. In addition, the time-dependent DFT calculations based on these geometries suggested that the thermally activated delayed fluorescence process of o-3CzBN is governed more by the higher-lying excited states than by the structural changes in the excited states.<br>


2003 ◽  
Vol 68 (1) ◽  
pp. 89-104 ◽  
Author(s):  
Stanislav Záliš ◽  
Antonín Vlček ◽  
Chantal Daniel

This contribution presents the results of the TD-DFT and CASSCF/CASPT2 calculations on [W(CO)4(MeDAB)] (MeDAB = N,N'-dimethyl-1,4-diazabutadiene), [W(CO)4(en)] (en = ethylenediamine), [W(CO)5(py)] (py = pyridine) and [W(CO)5(CNpy)] (CNpy = 4-cyanopyridine) complexes. Contrary to the textbook interpretation, calculations on the model complex [W(CO)4(MeDAB)] and [W(CO)5(CNpy)] show that the lowest W→MeDAB and W→CNpy MLCT excited states are immediately followed in energy by several W→CO MLCT states, instead of ligand-field (LF) states. The lowest-lying excited states of [W(CO)4(en)] system were characterized as W(COeq)2→COax CT excitations, which involve a remarkable electron density redistribution between axial and equatorial CO ligands. [W(CO)5(py)] possesses closely-lying W→CO and W→py MLCT excited states. The calculated energies of these states are sensitive to the computational methodology used and can be easily influenced by a substitution effect. The calculated shifts of [W(CO)4(en)] stretching CO frequencies due to excitation are in agreement with picosecond time-resolved infrared spectroscopy experiments and confirm the occurrence of low-lying M→CO MLCT transitions. No LF electronic transitions were found for either of the complexes studied in the region up to 4 eV.


2014 ◽  
Vol 18 (06) ◽  
pp. 475-492 ◽  
Author(s):  
Neha Agnihotri ◽  
Ronald P. Steer

The molecular orbital energies and symmetries, electronic state energies and symmetries, and orbital compositions and oscillator strengths for one-photon radiative transitions up to an energy of 4 eV have been calculated by DFT and TD-DFT methods for 15 d0 and d10 metalloporphyrins. Data for both singlet and triplet excited states are reported and used to identify potential candidates for use as photon upconverters by homomolecular triplet–triplet annihilation.


2017 ◽  
Vol 16 (4) ◽  
pp. 539-546 ◽  
Author(s):  
C. Rémy ◽  
C. Allain ◽  
I. Leray

A series of π conjugated naphthalimide derivatives were prepared. Compounds display efficient photoinduced charge transfer in solution which was rationalized by time-resolved spectroscopy and modelled by TD-DFT calculations.


2014 ◽  
Vol 53 (13) ◽  
pp. 6624-6633 ◽  
Author(s):  
Jamal Moussa ◽  
Lise-Marie Chamoreau ◽  
Alessandra Degli Esposti ◽  
Maria Pia Gullo ◽  
Andrea Barbieri ◽  
...  

1997 ◽  
Vol 51 (4) ◽  
pp. 580-583 ◽  
Author(s):  
Pingyun Chen ◽  
Richard A. Palmer

Ten-nanosecond time resolution has been achieved with step-scan FT-IR absorbance difference spectroscopy (S2FT-IR Δ A TRS) and demonstrated by measuring Δ A spectra of fac-[Re(bpy)(CO)3Cl] and cis-[Os(bpy)2(CO)(4,4′-bpy)]2+ (bpy = 2,2′-bipyridine; 4,4′-bpy=4,4′-bipyridine) in CH3CN solution, following 355-nm laser excitation. In both complexes, the large shifts in (CO) to higher energy are consistent with the assignment that the lowest-energy excited states are metal-to-ligand charge transfer in nature. For [Os(bpy)2(CO)(4,4′-bpy)]2+, it is also possible to measure the excited-state decay kinetics, again with 10-ns resolution. In addition, Δ A bands are observed that are related to excited-state vibrations of the bipyridine ligands. Δ A spectra of good signal-to-noise ratio can be obtained for complexes with lifetimes as short as 10 ns.


2014 ◽  
Vol 43 (47) ◽  
pp. 17703-17711 ◽  
Author(s):  
Sergey Ketkov ◽  
Nikolai Isachenkov ◽  
Elena Rychagova ◽  
Wen-Bih Tzeng

The influence of the (η6-arene)2M (M = Cr, V, Cr+) composition on parameters of intravalency and Rydberg transitions is explained on the basis of time-dependent DFT.


2014 ◽  
Vol 5 (11) ◽  
pp. 1806-1811 ◽  
Author(s):  
Fabrizio Santoro ◽  
Roberto Improta ◽  
Tobias Fahleson ◽  
Joanna Kauczor ◽  
Patrick Norman ◽  
...  

2020 ◽  
Author(s):  
Masaki Saigo ◽  
Kiyoshi Miyata ◽  
Hajime Nakanotani ◽  
Chihaya Adachi ◽  
Ken Onda

We have investigated the solvent-dependence of structural changes along with intersystem crossing of a thermally activated delayed fluorescence (TADF) molecule, 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (o-3CzBN), in toluene, tetrahydrofuran, and acetonitrile solutions using time-resolved infrared (TR-IR) spectroscopy and DFT calculations. We found that the geometries of the S1 and T1 states are very similar in all solvents though the photophysical properties mostly depend on the solvent. In addition, the time-dependent DFT calculations based on these geometries suggested that the thermally activated delayed fluorescence process of o-3CzBN is governed more by the higher-lying excited states than by the structural changes in the excited states.<br>


2014 ◽  
Vol 43 (47) ◽  
pp. 17820-17827 ◽  
Author(s):  
Elena N. Golubeva ◽  
Ekaterina M. Zubanova ◽  
Michail Ya. Melnikov ◽  
Fedor E. Gostev ◽  
Ivan V. Shelaev ◽  
...  

Photoinduced processes of tetrahexylammonium tetrachlorocuprate [(C6H13)4N]2CuIICl4 in chloro-organic solvents were investigated by steady state photolysis and femtosecond transient absorption spectroscopy, as well as TD-DFT calculations of excited terms.


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