scholarly journals Interaction of Triplet Excited States of Ketones with Nucleophilic Groups: (π,π*) and (n,π*) versus (σ*,π*) States. Substituent-Induced State Switching in Triplet Ketones

2017 ◽  
Vol 70 (4) ◽  
pp. 387 ◽  
Author(s):  
Götz Bucher
Keyword(s):  
Excited State ◽  
Excited States ◽  
Intramolecular Interaction ◽  
Triplet States ◽  
Triplet Excited State ◽  
Excitation Energies ◽  
Exciplex Formation ◽  
Lone Pairs ◽  
Triplet Excited States ◽  
Spin Densities

The intramolecular interaction of ketone triplet excited states with nucleophilic substituents is investigated by studying the electronic properties of phenalenone and a range of phenalenones functionalized in position 9 as a model system. In accordance with the literature, a (π,π*) triplet excited state is predicted for phenalenone. Similarly, 9-fluoro-, 9-chloro-, and 9-methoxyphenalenone are calculated to have (π,π*) lowest triplet excited states, whereas the lowest triplet states of 9-bromo-, 9-iodo, 9-methylthio, and 9-dimethylaminophenalenone are predicted to have (σ*,π*) character. As a result of the interaction between halogen and oxygen lone pairs increasing with increasing orbital size, the antibonding linear combination of substituent lone pairs with oxygen lone pairs sufficiently rises in energy to change the character of the lowest triplet excited state of the 9-substituted phenalenones from (π,π*) to (σ*,π*). These unusual triplet excited states or exciplexes should essentially behave like (n,π*) triplets states, but will differ from pure (n,π*) states by showing significant spin densities at the substituent heteroatoms, predicted to reach values of 0.25 for 9-iodophenalenone, and ~0.5 for 9-dimethylaminophenalenone. Vertical T1–T2 excitation energies calculated indicate that the stabilization of the (σ*,π*) relative to the (π,π*) state can reach 1 eV. Preliminary calculations on the triplet excited states of 2-iodobenzophenone, 4-iodo-2-butanone, and iodoacetone indicate that intramolecular triplet exciplex formation should be a general phenomenon, as long as the ring being formed is at least a five-membered ring.

scholarly journals Orthogonally Aligned Cyclic BODIPY Arrays with Long-lived Triplet Excited States as Efficient Heavy-Atom-Free Photosensitizers

2021 ◽  
Author(s):  
Zhaoyang Zhu ◽  
Xue Zhang ◽  
Xing Guo ◽  
Qing-Hua Wu ◽  
Zhongxin Li ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Energy Transfer ◽  
Excited State ◽  
Excited States ◽  
Heavy Atom ◽  
Triplet Excited State ◽  
Transfer Processes ◽  
Excited State Lifetimes ◽  
Triplet Excited States

Photosensitizers with long triplet excited state lifetimes are key to their efficient electron transfer or energy transfer processes. Herein, we report a novel class of cyclic trimeric BODIPY arrays which...

Preparation of Bodipy–ferrocene dyads and modulation of the singlet/triplet excited state of bodipy via electron transfer and triplet energy transfer

2016 ◽  
Vol 4 (14) ◽  
pp. 2843-2853 ◽  
Author(s):  
Xueyan Wu ◽  
Wenting Wu ◽  
Xiaoneng Cui ◽  
Jianzhang Zhao ◽  
Mingbo Wu
Keyword(s):  
Electron Transfer ◽  
Energy Transfer ◽  
Excited State ◽  
Excited States ◽  
Singlet Excited State ◽  
Triplet Excited State ◽  
Triplet Energy ◽  
Triplet Excited States ◽  
Triplet Energy Transfer

Bodipy–ferrocene dyads were prepared for reversible electrochemical switching of the singlet excited state (fluorescence), as well as the triplet excited states of Bodipy.

scholarly journals Tuning the singlet-triplet energy gap: a unique approach to efficient photosensitizers with aggregation-induced emission (AIE) characteristics

2015 ◽  
Vol 6 (10) ◽  
pp. 5824-5830 ◽  
Author(s):  
Shidang Xu ◽  
Youyong Yuan ◽  
Xiaolei Cai ◽  
Chong-Jing Zhang ◽  
Fang Hu ◽  
...  
Keyword(s):  
Excited State ◽  
Excited States ◽  
Energy Gap ◽  
Intersystem Crossing ◽  
Triplet Excited State ◽  
Triplet Energy ◽  
Aggregation Induced Emission ◽  
Unique Approach ◽  
Triplet Excited States

The efficiency of the intersystem crossing process can be improved by reducing the energy gap between the singlet and triplet excited states (ΔEST), which offers the opportunity to improve the yield of the triplet excited state.

scholarly journals Inverting singlet and triplet excited states using strong light-matter coupling

2019 ◽  
Vol 5 (12) ◽  
pp. eaax4482 ◽  
Author(s):  
Elad Eizner ◽  
Luis A. Martínez-Martínez ◽  
Joel Yuen-Zhou ◽  
Stéphane Kéna-Cohen
Keyword(s):  
Excited States ◽  
Delayed Fluorescence ◽  
Triplet States ◽  
Excitation Energies ◽  
Strong Light ◽  
Strongly Coupled ◽  
Matter Coupling ◽  
Level Shifts ◽  
Molecular Excitation ◽  
Triplet Excited States

In organic microcavities, hybrid light-matter states can form with energies that differ from the bare molecular excitation energies by nearly 1 eV. A timely question, given the recent advances in the development of thermally activated delayed fluorescence materials, is whether strong light-matter coupling can be used to invert the ordering of singlet and triplet states and, in addition, enhance reverse intersystem crossing (RISC) rates. Here, we demonstrate a complete inversion of the singlet lower polariton and triplet excited states. We also unambiguously measure the RISC rate in strongly coupled organic microcavities and find that, regardless of the large energy level shifts, it is unchanged compared to films of the bare molecules. This observation is a consequence of slow RISC to the lower polariton due to the delocalized nature of the state across many molecules and an inability to compete with RISC to the dark exciton reservoir.

scholarly journals Exploitation of Baird Aromaticity and Clar’s Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

Chemistry ◽  
2021 ◽  
Vol 3 (2) ◽  
pp. 532-549
Author(s):  
Felix Plasser
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Density Functional ◽  
Materials Science ◽  
Chemical Shifts ◽  
Qualitative Description ◽  
Triplet States ◽  
Excitation Energies ◽  
Polycyclic Aromatic

Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four biphenylene-derived PAHs finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). The results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

Effects of extending the π-conjugation of the acetylide ligand on the photophysics and reverse saturable absorption of Pt(ii) bipyridine bisacetylide complexes

2016 ◽  
Vol 18 (41) ◽  
pp. 28674-28687 ◽  
Author(s):  
Taotao Lu ◽  
Chengzhe Wang ◽  
Levi Lystrom ◽  
Chengkui Pei ◽  
Svetlana Kilina ◽  
...  
Keyword(s):  
Excited State ◽  
Excited States ◽  
Substituent Effect ◽  
Excited State Absorption ◽  
Saturable Absorption ◽  
Reverse Saturable Absorption ◽  
Triplet Excited State ◽  
Near Ir ◽  
Terminal Substituent ◽  
Acetylide Ligand

Extending the acetylide ligand π-conjugation diminishes the terminal substituent effect on the lowest excited states, but expands the triplet excited-state absorption to the near-IR region.

Multiconfiguration pair-density functional theory for doublet excitation energies and excited state geometries: the excited states of CN

2017 ◽  
Vol 19 (44) ◽  
pp. 30089-30096 ◽  
Author(s):  
Jie J. Bao ◽  
Laura Gagliardi ◽  
Donald G. Truhlar
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Excited States ◽  
Density Functional ◽  
Excitation Energies ◽  
Functional Theory ◽  
Pair Density

MC-PDFT is more accurate than CR-EOM-CCSD(T) or TDDFT when averaged over the first four adiabatic excitation energies of CN.

scholarly journals 0+ States of 8Be

1968 ◽  
Vol 21 (3) ◽  
pp. 239 ◽  
Author(s):  
FC Barker ◽  
HJ Hay ◽  
PB Treacy
Keyword(s):  
Excited State ◽  
Excited States ◽  
Cross Section ◽  
Scattering Data ◽  
Excitation Energies ◽  
R Matrix ◽  
Channel Radius

The light even nuclei with A ;;;. 10 have 0+ excited states near 6 MeV, probably with large (X-particle reduced widths. A similar state in BBe would be very broad. Evidence for 0+ excited states in BBe has been obtained here using many-level R-matrix fits to known (X-(X scattering data, but the excitation energies depend strongly on the assumed channel radius. For a simultaneous fit to the 9Be(p, d)BBe cross section, assuming these higher states are not strongly populated, the channel radius is restricted to (7~~) fm, implying a 0+ excited state at (6=f3) MeV of width (9=f4) MeV.

scholarly journals Exploitation of Baird Aromaticity and Clar's Rule for Tuning the Triplet Energies of Polycyclic Aromatic Hydrocarbons

2021 ◽  
Author(s):  
Felix Plasser
Keyword(s):  
Polycyclic Aromatic Hydrocarbons ◽  
Excited States ◽  
Aromatic Hydrocarbons ◽  
Density Functional ◽  
Materials Science ◽  
Chemical Shifts ◽  
Qualitative Description ◽  
Triplet States ◽  
Excitation Energies ◽  
Polycyclic Aromatic

Polycyclic aromatic hydrocarbons (PAH) are a prominent substance class with a variety of applications in molecular materials science. Their electronic properties crucially depend on the bond topology in ways that are often highly non-intuitive. Here, we study, using density functional theory, the triplet states of four PAHs based on the biphenylene motif finding dramatically different triplet excitation energies for closely related isomeric structures. These differences are rationalised using a qualitative description of Clar sextets and Baird quartets, quantified in terms of nucleus independent chemical shifts, and represented graphically through a recently developed method for visualising chemical shielding tensors (VIST). These results are further interpreted in terms of a 2D rigid rotor model of aromaticity and through an analysis of the natural transition orbitals involved in the triplet excited states showing good consistency between the different viewpoints. We believe that this work constitutes an important step in consolidating these varying viewpoints of electronically excited states.

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