Excited State Dynamics of Perylenediimide films with Isopropyl phenyl- and Undecane-Substitution

The aggregation of Perylene Diimide (PDI) and its derivatives strongly depends on the molecular structure, and therefore has great impact on the excited states. By regulating the molecular stacking such as monomer, dimer, J- and/or H-aggregate, the formation of different excited states is adjustable and controllable. In this study, we have synthesized two kinds of PDI derivatives - undecane-substituted PDI (PDI-1) and diisopropylphenyl-substituted PDI (PDI-2), and the films are fabricated with spin-coating method. By employing photoluminescence (PL), time-resolved photoluminescence (TRPL) and transient absorption (TA) spectroscopy, the excited-state dynamics of two PDI amorphous films have been investigated systematically. The result reveals that both films have formed excimer after photoexcitation mainly due to the stronger electronic coupling among molecule aggregate in the amorphous film. It should be noted that the excited state dynamics in PDI-2 shows a singlet fission like process, which is evidenced by the appearance of triplet state absorption. This study provides the dynamics of excited state in amorphous PDI films, and pave the way for better understanding and adjusting the excited state of amorphous films.

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Impact of Side-Chain Substituents on the Excited State Dynamics of Perylene Diimide Amorphous Films

10.26434/chemrxiv.12821492.v1 ◽

2020 ◽

Author(s):

Qiu-Shi Ma ◽

Cheng-Wei Ju ◽

Ruihua Pu ◽

Wenjie Zhang ◽

Xian Lin ◽

...

Keyword(s):

Excited State ◽

Triplet State ◽

Transient Absorption ◽

Excited State Absorption ◽

Perylene Diimide ◽

Side Chain ◽

Significant Feature ◽

Singlet Fission ◽

Amorphous Films ◽

Excited State Dynamics

Side-chain substitutions have important influence on the aggregation of perylene diimide (PDI), which show a great impact on their excited-state dynamics as well. Herein, by employing photoluminescence (PL), time-resolved photoluminescence (TRPL) and transient absorption (TA) spectroscopy, we investigated excited-state dynamics of two perylene diimide (PDI) derivative amorphous films, i.e. undecane-substituted PDI (PDI-1) and diisopropylphenyl-substituted PDI (PDI-2), fabricated with spin coating method. Femtosecond transient absorption spectra reveal that both films show pronounced ground state bleach (GSB) with lifetime longer than 10 ns while the relaxation of excited state absorption (ESA) has typical lifetime less than 1 ns. The significant feature of excited state decay in PDI-2 is dominated by transforming the singlet excited state into two triplet states via singlet fission, which is evidenced by the appearance of triplet state absorption. By contrast, the absence of triplet state absorption and the appearance of long-lived emission species in PDI-1 suggest that the decay of excited-like state could be dominated by the formation of excimer. Our present study reveals for the first time that the singlet fission does occur in amorphous PDI film, the study also demonstrates that side-chain substitutions have great impact on the excited-state dynamics of PDI.

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Excited-State Dynamics in the RNA Nucleotide Uridine 5’-Monophosphate Investigated by Femtosecond Broadband Transient Absorption Spectroscopy

10.26434/chemrxiv.7860023 ◽

2019 ◽

Author(s):

Matthew M. Brister ◽

Carlos Crespo-Hernández

Keyword(s):

Excited State ◽

Excited States ◽

Ground State ◽

Transient Absorption ◽

Electronic Energy ◽

Transient Absorption Spectroscopy ◽

Electronic Relaxation ◽

Vibrationally Excited ◽

Excited State Dynamics ◽

Π State

Damage to RNA from ultraviolet radiation induce chemical modifications to the nucleobases. Unraveling the excited states involved in these reactions is essential, but investigations aimed at understanding the electronic-energy relaxation pathways of the RNA nucleotide uridine 5’-monophosphate (UMP) have not received enough attention. In this Letter, the excited-state dynamics of UMP is investigated in aqueous solution. Excitation at 267 nm results in a trifurcation event that leads to the simultaneous population of the vibrationally-excited ground state, a longlived 1nOπ* state, and a receiver triplet state within 200 fs. The receiver state internally convert to the long-lived 3ππ* state in an ultrafast time scale. The results elucidate the electronic relaxation pathways and clarify earlier transient absorption experiments performed for uracil derivatives in solution. This mechanistic information is important because long-lived nπ* and ππ* excited states of both singlet and triplet multiplicities are thought to lead to the formation of harmful photoproducts.

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Investigation of ultrafast excited state dynamics of 2,2′,4,4′,6,6′-hexanitrostilbene using femtosecond transient absorption spectroscopy

RSC Advances ◽

10.1039/c4ra08305a ◽

2014 ◽

Vol 4 (104) ◽

pp. 60382-60385 ◽

Cited By ~ 4

Author(s):

Genbai Chu ◽

Min Shui ◽

Ying Xiong ◽

Jing Yi ◽

Kemei Cheng ◽

...

Keyword(s):

Excited State ◽

Excited States ◽

Absorption Spectroscopy ◽

Transient Absorption ◽

Transient Absorption Spectroscopy ◽

Excited State Dynamics ◽

Femtosecond Transient Absorption ◽

Femtosecond Transient Absorption Spectroscopy

A study on the dynamics and structures of the excited states of 2,2′,4,4′,6,6′-hexanitrostilbene shows equilibrium between vibrationally hot S1 (S*1) and S1 states with lifetimes of 0.8 and 6 ps, respectively.

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Spectroscopic investigation of excitonic and charge photogeneration processes in organic photovoltaic cells

10.26686/wgtn.17018834 ◽

2021 ◽

Author(s):

◽

Joseph Gallaher

Keyword(s):

Excited States ◽

Charge Separation ◽

Transient Absorption ◽

Mirror Image ◽

Triplet Exciton ◽

Organic Photovoltaic ◽

Charge Generation ◽

Time Resolved ◽

Blend Morphology ◽

Time Resolved Photoluminescence

Organic photovoltaic (OPV) cells show significant promise as a renewable energy resource capable of meeting the world’s large and growing energy needs. Increasing device efficiency is central to achieving an economically viable option for widespread applications. To this end, a better understanding of the structure and dynamics of the electronic excited states is needed. In particular, the mechanism by which excitons (electron-hole pairs) escape their Coulombic attraction and generate photocurrent is yet to be established. In this thesis ultrafast laser spectroscopy, in particular transient absorption and time-resolved photoluminescence, are used to study: exciton relaxation, morphological effects on charge separation, and the pathway leading to triplet exciton states. In Chapter 3, a series of oligothiophenes are synthesised with well-defined conjugation lengths to act as molecular models of polymer backbone sub-units, and thereby probe exciton relaxation processes. Time-resolved photoluminescence (TRPL) and transient absorption (TA) spectroscopy measurements presented in Chapter 4 reveal emission signatures evolve from a mirror image of absorption - which lacks vibronic structure - towards a spectrally narrower and vibronically structured species on the hundreds of femtosecond to early picosecond timescale. Analysis of this spectral evolution shows that a broad distribution of torsional conformers is driven to rapidly planarize in the excited state, including in solid films. This provides evidence that both torsional relaxation and energy migration could contribute to the non-mirror image absorption-emission spectra observed in polymer thin films. Recently, long lived TA signatures have been attributed to triplet excited states with the suggested formation pathway being similar to organic light emitting diodes, whereby non-geminate (bimolecular) charge recombination leads to the formation of both singlet and triplet states. Isolated oligothiophenes in solution provide an ideal model system to investigate the role of structural relaxation on triplet exciton formation. Through analysis of TA spectral dynamics in Chapter 5, singlet and triplet exciton populations were tracked. Restriction of the torsional relaxation increased triplet yield suggesting vibrational hot states could drive triplet formation. This model could aid in understanding triplet exciton formation in polymer-based solar cells via spin-mixing instead of non-geminate recombination. In a series of polymer:fullerene blends, the link between the nature of polymerfullerene intermixing and charge generation pathways was investigated. It is shown in Chapter 6 that free charge generation is most efficient in a 3-phase morphology that features intimately mixed polymer:fullerene regions amongst neat polymer and fullerene phases. Distinct spectroscopic signatures made it possible to determine whether holes occupy disordered or crystalline polymer chains. TA spectral dynamics reveal the migration of holes from intermixed to pure olymer regions in 3-phase morphology blends, which contrasted with observations in 2-phase blends. The energy gradient between the intermixed and phase-pure regions may be sufficient to drive efficient separation of charge pairs initially generated in intermixed regions, with free charges subsequently percolating through these phase-pure domains. The photophysics of a high performance polymer:polymer blend is studied in Chapter 7 in an effort to elucidate how these blends can rival their polymer:fullerene counterparts. Optical spectroscopy reveals incomplete exciton dissociation and rapid geminate recombination in the blends. This is shown to result from a largely phase-separated morphology with domains greater than the exciton diffusion length. Significant loss of charge carriers on early timescales highlights increasing polymer: polymer solar cell efficiency requires optimizing blend morphology to realise facile charge separation. Taken together, this thesis presents a valuable spectroscopic insight into the pathway of efficient charge separation and the importance of both blend morphology and polymer structure.

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Excited-State Dynamics of Room-Temperature Phosphorescent Organic Materials Based on Monobenzil and Bisbenzil Frameworks

Materials ◽

10.3390/ma13173904 ◽

2020 ◽

Vol 13 (17) ◽

pp. 3904

Author(s):

Kaveendra Maduwantha ◽

Shigeyuki Yamada ◽

Kaveenga Rasika Koswattage ◽

Tsutomu Konno ◽

Takuya Hosokai

Keyword(s):

Excited State ◽

Density Functional ◽

Room Temperature ◽

Photophysical Properties ◽

Density Functional Theory Calculations ◽

Time Resolved ◽

Excited State Dynamics ◽

Unique Material ◽

Potential Applications ◽

Time Resolved Photoluminescence

Room-temperature phosphorescent (RTP) materials have been attracting tremendous interest, owing to their unique material characteristics and potential applications for state-of-the-art optoelectronic devices. Recently, we reported the synthesis and fundamental photophysical properties of new RTP materials based on benzil, i.e., fluorinated monobenzil derivative and fluorinated and non-fluorinated bisbenzil derivative analogues [Yamada, S. et al., Beilstein J. Org. Chem. 2020, 16, 1154–1162.]. To deeply understand their RTP properties, we investigated the excited-state dynamics and photostability of the derivatives by means of time-resolved and steady-state photoluminescence spectroscopies. For these derivatives, clear RTP emissions with lifetimes on the microsecond timescale were identified. Among them, the monobenzil derivative was found to be the most efficient RTP material, showing both the longest lifetime and highest amplitude RTP emission. Time-resolved photoluminescence spectra, measured at 77 K, and density functional theory calculations revealed the existence of a second excited triplet state in the vicinity of the first excited singlet state for the monobenzil derivative, indicative of the presence of a fast intersystem crossing pathway. The correlation between the excited state dynamics, emission properties, and conformational flexibility of the three derivatives is discussed.

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Excited-State Dynamics in the RNA Nucleotide Uridine 5’-Monophosphate Investigated by Femtosecond Broadband Transient Absorption Spectroscopy

10.26434/chemrxiv.7860023.v1 ◽

2019 ◽

Author(s):

Matthew M. Brister ◽

Carlos Crespo-Hernández

Keyword(s):

Excited State ◽

Excited States ◽

Ground State ◽

Transient Absorption ◽

Electronic Energy ◽

Transient Absorption Spectroscopy ◽

Electronic Relaxation ◽

Vibrationally Excited ◽

Excited State Dynamics ◽

Π State

Damage to RNA from ultraviolet radiation induce chemical modifications to the nucleobases. Unraveling the excited states involved in these reactions is essential, but investigations aimed at understanding the electronic-energy relaxation pathways of the RNA nucleotide uridine 5’-monophosphate (UMP) have not received enough attention. In this Letter, the excited-state dynamics of UMP is investigated in aqueous solution. Excitation at 267 nm results in a trifurcation event that leads to the simultaneous population of the vibrationally-excited ground state, a longlived 1nOπ* state, and a receiver triplet state within 200 fs. The receiver state internally convert to the long-lived 3ππ* state in an ultrafast time scale. The results elucidate the electronic relaxation pathways and clarify earlier transient absorption experiments performed for uracil derivatives in solution. This mechanistic information is important because long-lived nπ* and ππ* excited states of both singlet and triplet multiplicities are thought to lead to the formation of harmful photoproducts.

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Mode-specific excited-state dynamics of N-methylpyrrole

Physical Chemistry Chemical Physics ◽

10.1039/c9cp00113a ◽

2019 ◽

Vol 21 (26) ◽

pp. 14387-14393 ◽

Cited By ~ 4

Author(s):

Kyung Chul Woo ◽

Sang Kyu Kim

Keyword(s):

Excited State ◽

Physical Properties ◽

Excited States ◽

Time Resolved ◽

Excited State Dynamics

A picosecond time-resolved dynamics study unravels the photo-physical properties of N-methylpyrrole in excited-states in a mode-specific way.

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Excited-State Dynamics of Room-Temperature Phosphorescent Organic Materials Based on Monobenzil and Bisbenzil Frameworks

10.20944/preprints202007.0631.v1 ◽

2020 ◽

Author(s):

Kaveendra Maduwantha ◽

Shigeyuki Yamada ◽

Kaveenga Rasika Koswattage ◽

Tsutomu Konno ◽

Takuya Hosokai

Keyword(s):

Excited State ◽

Density Functional ◽

Room Temperature ◽

Photophysical Properties ◽

Density Functional Theory Calculations ◽

Time Resolved ◽

Excited State Dynamics ◽

Unique Material ◽

Potential Applications ◽

Time Resolved Photoluminescence

Room-temperature phosphorescent (RTP) materials have been attracted tremendous interest owing to their unique material characteristics and potential applications for state-of-the-art optoelectronic devices. Recently, we have reported a synthesis and fundamental photophysical properties of new RTP materials based on benzil, i.e., fluorinated monobenzil derivative and fluorinated and non-fluorinated bisbenzil derivative analogues [Yamada, S. et al, Beilstein J. Org. Chem. 2020, 16, 1154–1162.]. To further understand their RTP properties, here we investigated the excited-state dynamics and photostability of the derivatives by means of time-resolved and steady-state photoluminescence spectroscopies. For these derivatives, clear RTP emissions with lifetimes on the microsecond timescale were identified. Among them, the monobenzil derivative was found to be the most efficient RTP material, showing both the longest lifetime and highest amplitude RTP emission. Time-resolved photoluminescence spectra measured at 77 K and density functional theory calculations revealed the existence of a second excited triplet state in the vicinity of the first excited singlet state for the monobenzil derivative, indicative of the presence of a fast intersystem crossing pathway. A discussion of the correlation between the excited state dynamics, emission properties, and conformational flexibility of the three derivatives is presented.

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