Origin of dual emission in σ-bridged donor–acceptor TADF compounds

2019 ◽  
Vol 7 (40) ◽  
pp. 12601-12609 ◽  
Author(s):  
Rokas Skaisgiris ◽  
Tomas Serevičius ◽  
Karolis Kazlauskas ◽  
Yan Geng ◽  
Chihaya Adachi ◽  
...  
Keyword(s):  
Electronic Coupling ◽  
Dual Emission ◽  
Donor And Acceptor ◽  
Donor Acceptor

Minimization of electronic coupling between donor and acceptor units in σ-spaced TADF compounds leads to emergence of unexpected emission mechanisms, deteriorating TADF properties.

scholarly journals Thermochromic aggregation-induced dual phosphorescence via temperature-dependent sp3-linked donor-acceptor electronic coupling

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Tao Wang ◽  
Zhubin Hu ◽  
Xiancheng Nie ◽  
Linkun Huang ◽  
Miao Hui ◽  
...  
Keyword(s):  
Excited State ◽  
Room Temperature ◽  
Electronic Coupling ◽  
Temperature Dependent ◽  
Molecular Systems ◽  
Donor And Acceptor ◽  
Theoretical Investigations ◽  
Donor Acceptor ◽  
And Control ◽  
Two Temperature

AbstractAggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient room temperature phosphorescence (RTP) in bulk by restricting molecular motions. Here, we show that by utilizing triphenylamine (TPA) as an electronic donor that connects to an acceptor via an sp3 linker, six TPA-based AIE-active RTP luminophores were obtained. Distinct dual phosphorescence bands emitting from largely localized donor and acceptor triplet emitting states could be recorded at lowered temperatures; at room temperature, only a merged RTP band is present. Theoretical investigations reveal that the two temperature-dependent phosphorescence bands both originate from local/global minima from the lowest triplet excited state (T1). The reported molecular construct serves as an intermediary case between a fully conjugated donor-acceptor system and a donor/acceptor binary mix, which may provide important clues on the design and control of high-freedom molecular systems with complex excited-state dynamics.

scholarly journals Thermochromic AIE Dual Phosphorescence via Temperature-Dependent sp3-Linked Donor-Acceptor Electronic Coupling

2020 ◽  
Author(s):  
Tao Wang ◽  
Zhubin Hu ◽  
Xiancheng Nie ◽  
Linkun Huang ◽  
Hui Miao ◽  
...  
Keyword(s):  
Excited State ◽  
Room Temperature ◽  
Electronic Coupling ◽  
Triplet States ◽  
Molecular Motions ◽  
Temperature Dependent ◽  
Molecular Systems ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
And Control

<p>Aggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient RTP in bulk by restricting molecular motions. Here we show that by utilizing triphenylamine (TPA) as an electronic donor which connects to an acceptor via an sp3 linker, six TPA-based AIE-active RTP luminophores were obtained. Both the TPA AIE-gen and the <i>sp</i><sup>3</sup>-linkage can suppress aggregation-caused quenching. Consequently, dual phosphorescence bands emitting from localized donor and acceptor triplet states, respectively, could be recorded at lowered temperatures; at room temperature, only a single RTP band corresponding to the lowest triplet state is present, presumably due to thermally assisted electronic coupling between the two states. The reported molecular construct serves as an “intermediary case” between a fully conjugated donor-acceptor system and a do-nor/acceptor binary mix, which may provide important clues on the design and control of molecular systems with complex excited-state dynamics.<br></p>

scholarly journals Role of intramolecular hydrogen bonds in promoting electron flow through amino acid and oligopeptide conjugates

2021 ◽  
Vol 118 (11) ◽  
pp. e2026462118
Author(s):  
Rafał Orłowski ◽  
John A. Clark ◽  
James B. Derr ◽  
Eli M. Espinoza ◽  
Maximilian F. Mayther ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Hydrogen Bonds ◽  
Electron Flow ◽  
Intramolecular Hydrogen Bonding ◽  
Electronic Coupling ◽  
Molecular Architecture ◽  
Energy Flows ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
Intramolecular Hydrogen

Elucidating the factors that control charge transfer rates in relatively flexible conjugates is of importance for understanding energy flows in biology as well as assisting the design and construction of electronic devices. Here, we report ultrafast electron transfer (ET) and hole transfer (HT) between a corrole (Cor) donor linked to a perylene-diimide (PDI) acceptor by a tetrameric alanine (Ala)4. Selective photoexcitation of the donor and acceptor triggers subpicosecond and picosecond ET and HT. Replacement of the (Ala)4 linker with either a single alanine or phenylalanine does not substantially affect the ET and HT kinetics. We infer that electronic coupling in these reactions is not mediated by tetrapeptide backbone nor by direct donor–acceptor interactions. Employing a combination of NMR, circular dichroism, and computational studies, we show that intramolecular hydrogen bonding brings the donor and the acceptor into proximity in a “scorpion-shaped” molecular architecture, thereby accounting for the unusually high ET and HT rates. Photoinduced charge transfer relies on a (Cor)NH…O=C–NH…O=C(PDI) electronic-coupling pathway involving two pivotal hydrogen bonds and a central amide group as a mediator. Our work provides guidelines for construction of effective donor–acceptor assemblies linked by long flexible bridges as well as insights into structural motifs for mediating ET and HT in proteins.

scholarly journals Thermochromic AIE Dual Phosphorescence via Temperature-Dependent sp3-Linked Donor-Acceptor Electronic Coupling

2020 ◽  
Author(s):  
Tao Wang ◽  
Zhubin Hu ◽  
Xiancheng Nie ◽  
Linkun Huang ◽  
Hui Miao ◽  
...  
Keyword(s):  
Excited State ◽  
Room Temperature ◽  
Electronic Coupling ◽  
Triplet States ◽  
Molecular Motions ◽  
Temperature Dependent ◽  
Molecular Systems ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
And Control

<p>Aggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient RTP in bulk by restricting molecular motions. Here we show that by utilizing triphenylamine (TPA) as an electronic donor which connects to an acceptor via an sp3 linker, six TPA-based AIE-active RTP luminophores were obtained. Both the TPA AIE-gen and the <i>sp</i><sup>3</sup>-linkage can suppress aggregation-caused quenching. Consequently, dual phosphorescence bands emitting from localized donor and acceptor triplet states, respectively, could be recorded at lowered temperatures; at room temperature, only a single RTP band corresponding to the lowest triplet state is present, presumably due to thermally assisted electronic coupling between the two states. The reported molecular construct serves as an “intermediary case” between a fully conjugated donor-acceptor system and a do-nor/acceptor binary mix, which may provide important clues on the design and control of molecular systems with complex excited-state dynamics.<br></p>

Thermochromic AIE Dual Phosphorescence via Temperature-Dependent sp3-Linked Donor-Acceptor Electronic Coupling

2020 ◽  
Author(s):  
Tao Wang ◽  
Zhubin Hu ◽  
Xiancheng Nie ◽  
Linkun Huang ◽  
Hui Miao ◽  
...  
Keyword(s):  
Excited State ◽  
Room Temperature ◽  
Electronic Coupling ◽  
Triplet States ◽  
Molecular Motions ◽  
Temperature Dependent ◽  
Molecular Systems ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
And Control

<p>Aggregation-induced emission (AIE) has proven to be a viable strategy to achieve highly efficient RTP in bulk by restricting molecular motions. Here we show that by utilizing triphenylamine (TPA) as an electronic donor which connects to an acceptor via an sp3 linker, six TPA-based AIE-active RTP luminophores were obtained. Both the TPA AIE-gen and the <i>sp</i><sup>3</sup>-linkage can suppress aggregation-caused quenching. Consequently, dual phosphorescence bands emitting from localized donor and acceptor triplet states, respectively, could be recorded at lowered temperatures; at room temperature, only a single RTP band corresponding to the lowest triplet state is present, presumably due to thermally assisted electronic coupling between the two states. The reported molecular construct serves as an “intermediary case” between a fully conjugated donor-acceptor system and a do-nor/acceptor binary mix, which may provide important clues on the design and control of molecular systems with complex excited-state dynamics.<br></p>

scholarly journals Supramolecular Systems Containing B–N Frustrated Lewis Pairs of Tris(pentafluorophenyl)borane and Triphenylamine Derivatives

2021 ◽  
Vol 03 (02) ◽  
pp. 174-183
Author(s):  
P. Chidchob ◽  
S. A. H. Jansen ◽  
S. C. J. Meskers ◽  
E. Weyandt ◽  
N. P. van Leest ◽  
...  
Keyword(s):  
Materials Science ◽  
Supramolecular Polymers ◽  
Frustrated Lewis Pairs ◽  
Paramagnetic Resonance ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
Noncovalent Polymers ◽  
Electron Paramagnetic ◽  
Supramolecular Polymerization ◽  
Lewis Pairs

The introduction of a chemical additive to supramolecular polymers holds high potential in the development of new structures and functions. In this regard, various donor- and acceptor-based molecules have been applied in the design of these noncovalent polymers. However, the incorporation of boron–nitrogen frustrated Lewis pairs in such architectures is still rare despite their many intriguing properties in catalysis and materials science. The limited choices of suitable boron derivatives represent one of the main limitations for the advancement in this direction. Here, we examine the use of the commercially available tris(pentafluorophenyl)borane with various triphenylamine derivatives to create supramolecular B–N charge transfer systems. Our results highlight the importance of a proper balance between the donor/acceptor strength and the driving force for supramolecular polymerization to achieve stable, long-range ordered B–N systems. Detailed analyses using electron paramagnetic resonance and optical spectroscopy suggest that tris(pentafluorophenyl)borane displays complex behavior with the amide-based triphenylamine supramolecular polymers and may interact in dimers or larger chiral aggregates, depending on the specific structure of the triphenylamines.

Controlling charge transfer in fullerene/phthalocyanine electron donor-acceptor conjugates/hybrids

2009 ◽  
Vol 13 (10) ◽  
pp. 1034-1039 ◽  
Author(s):  
Wolfgang Seitz ◽  
Axel Kahnt ◽  
Dirk M. Guldi ◽  
Tomas Torres
Keyword(s):  
Three Dimensional ◽  
Reorganization Energy ◽  
Model Systems ◽  
Transfer Reactions ◽  
Dimensional Electron ◽  
Specific Composition ◽  
Donor And Acceptor ◽  
Donor Acceptor ◽  
Light Harvesting Antenna ◽  
Energetic Charge

Fullerenes and phthalocyanines are ideally suited for devising integrated, multi-component model systems to transmit and process solar energy. Implementation of C 60 as a three-dimensional electron acceptor bears great promises on account of its small reorganization energy in electron transfer reactions and has exerted a noteworthy impact on the improvement of light-induced charge separation. This mini-review describes how the specific composition of phthalocyanines chromophores associated with C 60 – yielding artificial light-harvesting antenna and reaction center mimics – have been elegantly utilized to tune the electronic couplings between donor and acceptor sites. Specifically, the effects that these parameters have on the rate, yield and lifetime of the energetic charge-separated states are considered.

scholarly journals Spectral fine tuning of cyanine dyes: electron donor–acceptor substituted analogues of thiazole orange

2015 ◽  
Vol 14 (9) ◽  
pp. 1703-1712 ◽  
Author(s):  
Elizabeth E. Rastede ◽  
Matteus Tanha ◽  
David Yaron ◽  
Simon C. Watkins ◽  
Alan S. Waggoner ◽  
...  
Keyword(s):  
Electron Donor ◽  
Emission Spectra ◽  
Fine Tuning ◽  
Cyanine Dye ◽  
Thiazole Orange ◽  
Absorption And Emission ◽  
Donor And Acceptor ◽  
Dye Absorption ◽  
Donor Acceptor ◽  
Electron Donor And Acceptor

Strategically placed electron donor and acceptor groups allow fine-tuning of cyanine dye absorption and emission spectra while preserving recognition of biomolecular hosts such as DNA and proteins.

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