Intrachain Energy Transfer Research Articles

Modulation of the photothermal degradation of epoxy upon ultraviolet irradiation by polyhedral oligomeric silsesquioxane: a multiscale simulation study

In this study, it was theoretically demonstrated that efficient intrachain energy transfer and robust network structure construction improved the UV resistance of the epoxy matrix.

Dynamic molecular conformational change leading to energy transfer in F8-5% BSP copolymer revealed by single-molecule spectroscopy.

Polyfluorene-based copolymers such as poly(9,9-dioctylfluorene)-alt-5% [bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4-phenylenediamine] (F8-5% BSP) are efficient blue-emitting polymers with various electronic phases: F8 blue-emitting glassy phase, F8 ordered more red-emitting β-phase, and F8/BSP charge transfer (CT) state. Polymer light-emitting device performance and color purity can be significantly improved by forming β-phase segments. However, the role of the β-phase on energy transfer (ET) among glassy F8, β-phase, and F8/BSP CT state is unclear. Herein, we identify dynamic molecular conformation-controlled ET from locally excited states to either the CT state or β-phase in light-emitting copolymers. By conducting single-molecule spectroscopy for single F8-5% BSP chains, we find inefficient intra-chain ET from glassy segments to the CT state, while efficient ET from the glassy to the β-phase. Spontaneous and reversible CT on-off emission is observed both in the presence and absence of the β-phase. The density functional theory calculations reveal the origin of the on-chain CT state and indicate this CT emission on-off switching behavior could be related to molecule torsional motion between BSP and F8 units. The population of the CT state by ET can be increased via through-space interaction between the F8 block and the BSP unit on a self-folded chain. Temperature-dependent single-molecule spectroscopy confirms such interaction showing a gradual increase in intensity of the CT emission with the temperature. Based on these observations, we propose the dynamic molecular motion-induced conformation change as the origin of the glassy-to-CT ET, and thermal energy may provide the activation for such a change to enhance the ET from glassy or β-phases to the CT state.

Slow Energy Transfer in Self‐Doped β‐Conformation Film of Steric Polydiarylfluorenes toward Stable Dual Deep‐Blue Amplified Spontaneous Emission

AbstractExciton behavior is crucial for improving the optoelectronic property of a light‐emitting conjugated polymer. Herein, the photoexcitation dynamics of exciton migration and energy transfer in a self‐doped β‐conformation film of the polydiarylfluorenes (poly[4‐(octyloxy)‐9,9‐diphenylfluoren‐2,7‐diyl]‐co‐[5‐(octyloxy)‐9,9‐ diphenylfluoren‐2,7‐diyl], PODPF) are demonstrated. Compared to the first generation of the β‐conformation polyfluorene, poly(9,9‐dioctylfluorene) (PFO), energy transfer occurs in PODPF β‐conformation films in a time period of ≈150 ps, much longer than those of the PFO ones (<5 ps), associated with the effective intrachain energy transfer (few hundred picoseconds), rather than interchain Förster energy transfer (a few picoseconds). Similar to PFO, the PODPF β‐conformation also displays well‐resolved vibronic emission peaks at 20 K, attributed to the planar and rigid conformation. Interestingly, a residual 0‐0 band emission of nonplanar conformation chain segments (435 nm, 2.85 eV) at 20 K also further confirms the exciton migration from the amorphous state to the β‐conformation domain in PODPF films. Therefore, the stable dual amplified spontaneous emission (ASE) behavior of the PODPF self‐doped films at 461 nm (2.69 eV) and 483 nm (2.57 eV), originates from the individual amorphous and β‐conformation domains.

Ultrafast study of inter‐ and intrachain energy transfer in a core–polymer

ABSTRACTInterchain interactions can play a positive role in reaching amplified spontaneous emission in an interesting core–polymer system where the donor (side chains) and the acceptor (core) are chemically linked together. Different degree of interchain interactions modifies the photophysical characteristics of the polymer. By means of transient absorption spectroscopy we show that the stimulated emission from the core decreases passing from solid state to concentrated solution and it is almost absent in the diluted solution. The conformational rearrangements of the core–polymer chain in solution limits the efficiency of the intrachain Förster energy transfer mechanism. The free chain rotations decrease the exciton hopping along the conjugated chains, the ratio between donor and acceptor moieties in the polymer, and change the relative orientation of the transition dipoles of the donor and acceptor causing a strong decrease of energy transfer efficiency and subsequently of the gain. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 965–969

Alternating donor–acceptor indigo-cyclopentadithiophene copolymers: competition between excited state conformational relaxation, energy transfer and excited state proton transfer

In a copolymer with indigo and CPDT, fast ESPT and/or intrachain energy transfer are observed whereas conformational relaxation is absent.

Photophysical properties of acetylene-linked syn bimane oligomers: a molecular photonic wire.

Computational studies using correlated wave function methods and density functional theory were carried out on a series of acetylene-linked bimane oligomers with particular emphasis on their excitonic properties and implications for intra-chain excitation energy transfer (EET). The low energy barriers found for the rotation of bimane subunits about the longitudinal axis are such that the π-conjugation is easily disrupted. Nevertheless, a distinctive feature of the oligomer lies in the parallel alignment of the S1 transition dipole along the longitudinal axis, which sustains electronic coupling between adjacent bimane subunits over a range of torsional angles and is crucial for driving intra-chain EET. Using a model that comprises hexameric donor and acceptor fragments, we evaluated electronic couplings and spectral overlaps, and applied Fermi's golden rule (in the weak electronic coupling regime) to approximate the lower limit of intra-chain EET in an acetylene-linked bimane photonic wire.

The role of chain conformation in energy transfer properties of single conjugated polymer molecule

Study of the relationship between conformation and photophysics of individual -conjugated polymer chain is one of the most important problems in polymer nanoscience and nanotechnology, which will facilitate the application of conjugated polymer in a range of electronic devices such as organic field-effect transistors, light-emitting diodes, and solar cells. Single-molecule spectroscopy has emerged as a powerful tool to unravel structure and dynamic heterogeneities that are hidden in ensemble average. Identification of the emitting segments through fluorescence of single conjugated polymer molecules and their dependence on the conformation can help reveal the mechanism and the extent of energy transfer process in a single polymer chain. In this paper, the photophysical properties of individual poly[2, 7-(9, 9-dioctylfluorene)-alt-4, 7-bis(thiophen-2-yl) benzo-2, 1, 3-thiadiazole] (PFO-DBT) conjugated polymer molecules are measured based on the defocused wide-field microscopy of single molecules. The single PFO-DBT molecules are prepared on cleaned glass coverslips by spin-coating solution of poly[methyl methacrylate] (PMMA) containing 110-9 mol/L PFO-DBT molecules in chloroform and toluene, respectively. Defocused imaging of single conjugated polymer molecule is performed based on a wide-field fluorescence microscope system. The change of defocused patterns of individual polymer chain maps the angular distribution of emitted chromophore and thus the emitting dipole orientation. Fluorescence trajectory and corresponding emission dipole moments of single conjugated polymer molecules are analyzed to identify the emitting conjugated segments. It is found that single PFO-DBT conjugated polymer molecules prepared by chloroform solvent show extended conformation. The intrachain energy transfer is dominant in the single conjugated polymer molecules that take extended conformation, which leads to photophysical properties of multiple chromophores. In contrast, single PFO-DBT conjugated polymer molecules prepared by toluene solvent hold folded conformation, which exhibit emission from single chromophore due to efficient interchain energy transfer. The emitting chromophore is not constant in a single PFO-DBT conjugated polymer molecule with folded conformation. About 35% of the single conjugated molecules prepared with toluene show only one constant emitting chromophore before photobleaching. However, about 65% of single conjugated polymer molecules prepared with toluene show two or more sequencely emitting chromophores. It can be concluded that the energy transfer properties of single PFO-DBT conjugated polymer molecule is greatly dependent on the conformation, which can be reflected in its photophysical properties. The study on the influence of single conjugated polymer conformation on energy transfer efficiency can provide the reference for the preparation and performance of optoelectronic devices and molecular devices based on conjugated polymer.

Triazolobenzothiadiazole‐Based Copolymers for Polymer Light‐Emitting Diodes: Pure Near‐Infrared Emission via Optimized Energy and Charge Transfer

A series of new near‐infrared (NIR) emitting copolymers, based on a low band gap 6‐(2‐butyloctyl)‐4,8‐di(thiophen‐2‐yl)‐[1,2,3]triazolo[4′,5′:4,5]benzo[1,2‐c]‐[1,2,5]thiadiazole (TBTTT) fluorophore copolymerized into a high band gap poly[3,3′‐ditetradecyl‐2,2′‐bithiophene‐5,5′‐diyl‐alt‐5‐(2‐ethylhexyl)‐4H‐thieno[3,4‐c]pyrrole‐4,6(5H)‐dione‐1,3‐diyl] (P2TTPD) host backbone, for polymer light‐emitting diode (PLED) applications is reported. PLEDs fabricated from the host polymer (P2TTPD‐0) show external quantum efficiencies (EQEs) up to 0.49% at 690 nm, with turn‐on voltage (Von) at only 2.4 V. By incorporating the TBTTT segments into the host polymer backbone, pure NIR emission peaking at ca. 900 nm is obtained with Von remaining below 5 V. This work demonstrates that such a low Von can be attributed to efficient intrachain energy and/or charge transfer to the TBTTT sites. When the NIR emitting copolymer (P2TTPD‐10) is blended with P2TTPD‐0, the TBTTT are confined to well‐separated polymer chains. As a result, the EQE from the blend is lower and the Von higher than that obtained from the pure copolymer (P2TTPD‐1.0) with equal content of TBTTT. An analogous copolymer (P4T‐1.0), consisting of poly[3,3′‐ditetradecyl‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene‐5,5′′′‐diyl] (P4T) as the host and 1% TBTTT as the NIR emitter, further demonstrates that pure NIR emission can be obtained only through optimized molecular orbital energy levels, as in P2TTPD‐1.0, which minimizes chances for either charge trapping or exciton splitting.

Energy Transfer Between Squaraine Polymer Sections: From Helix to Zigzag and All the Way Back.

We provide a joint experimental and theoretical study of squaraine polymers in solution. The absorption spectra show evidence that two different conformations are present in the polymer: a helix and a zigzag structure. This unique situation allows investigating ultrafast energy-transfer processes between different structural segments within a single polymer chain in solution. The understanding of the underlying dynamics is of fundamental importance for the development of novel materials for light-harvesting and optoelectronic applications. Here, we combine femtosecond transient absorption spectroscopy with time-resolved 2D electronic spectroscopy in order to demonstrate that ultrafast energy transfer within the squaraine polymer chains proceeds from initially excited helix segments to zigzag segments or vice versa, depending on the solvent as well as on the excitation wavenumber. These observations contrast other conjugated polymers such as MEH-PPV where much slower intrachain energy transfer was reported. The reason for the very fast energy transfer in squaraine polymers is most likely a close matching of the density of states between donor and acceptor polymer segments because of the very small reorganization energy in these cyanine-like chromophores.

Polynorbornene copolymer with side-chain triarylborane and iridium(III) groups: An emissive layer material with electron transporting properties for PhOLEDs

Vinyl-type polynorbornene copolymers (P1–P3) containing side-chain triarylborane and iridium moieties were prepared by palladium(II) catalyzed copolymerization of norbornene monomers bearing triarylborane (Mes2BPh, M1) and an iridium emitter ((ppy)2Ir(acac), ppy = 2-phenyl-pyridinato-C2,N; acac = acetylacetonato, M2). Copolymerization led to facile incorporation of the comonomers in a controlled manner depending on the feed ratio of the comonomers (4.0 mol%-Ir in P1; 6.7 mol%-Ir in P2; 12.4 mol%-Ir in P3). While solution PL spectra of the copolymers exhibited partial intra-chain energy transfer from the borane moiety to iridium, complete energy transfer occurred in the rigid matrix, such as at 77 K and in the film state. The LUMO level of the borane moiety (M1) was estimated to be 2.4 eV, which is lower than that of M2 and poly(N-vinylcarbazole) (PVK) (ca. 2.2 eV for both). Solution processed PhOLEDs (D1−D3) incorporating P1–P3 as an emissive material in the PVK host displayed good performance in the low current density region, but D1−D3 suffered severe efficiency roll-off with increasing current densities. Comparable performance of D2 with the device (D4) based on P2 emitter and PVK:PBD (2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole) host suggested that a borane moiety in the emissive polymer chain plays an actual role in facilitating electron transport in the emissive layer.

Energy transfer in PPV-based conjugated polymers: a defocused widefield fluorescence microscopy study

Both pendant and main chain conjugated MEH-PPV based polymers have been studied at the level of single chains using confocal and widefield fluorescence microscopy techniques. In particular, defocused widefield fluorescence is applied to reveal the extent of energy transfer in these polymers by identifying whether they act as single emitters. For main chain conjugated MEH-PPV, molecular weight and the surrounding matrix play a primary role in determining energy transport processes and whether single emitter behaviour is observed. Surprisingly in polymers with a saturated backbone but containing the same pendant MEH-PPV oligomer on each repeating unit, intra-chain energy transfer to a single emitter is also apparent. The results imply there is chromophore heterogeneity that can facilitate energy funneling to the emitting site. Both main chain conjugated and pendant MEH-PPV polymers exhibit changes in orientation of the emission dipole during a fluorescence trajectory of many seconds, whereas a model MEH-PPV oligomer does not. The results suggest that, in the polymers, the nature of the emitting chromophores can change during the time trajectory.

Excited-State Dynamics and Self-Organization of Poly(3-hexylthiophene) (P3HT) in Solution and Thin Films

The fluorescence decays of a stereoregular head-to-tail RR-HT poly(3-hexylthiophene), P3HT, in methylcyclohexane (MCH) are described by sums of three or four exponential terms, respectively above and below -10 °C. In the high-temperature region, the polymer lifetime (ca. 500 ps) is accompanied by two shorter decay times (ca. 20 and 120 ps), which are assigned to intrachain energy transfer from high to lower energy excitons on the basis of temperature and wavelength dependence of the fluorescence decays. The absence of conformational (torsional) relaxation is attributed to the small dihedral angle between monomers that is predicted for the stereoregular polymer in the ground state. Below -10 °C, the polymer forms excimer-like aggregates, showing vibrational structured absorption and emission bands similar to those observed in thin films. The vibrational structure is attributed to a deep minimum in the ground-state energy surface of the dimer or aggregate. Below -40 °C, the fluorescence measured at the aggregate emission wavelength (670 nm) basically results from direct excitation of the aggregate and decays with a sum of three exponential terms (decay times of ca. 0.14, 0.6, and 1.5 ns, with similar weights). Because the spectral similarities between film and aggregates indicate similar electronic first singlet excited states (and oscillator strengths), the much shorter decay times (0.05, 0.15, and 0.43 ns) and lower fluorescence quantum yield of P3HT in films are assigned to efficient exciton dissociation and/or phonon-induced internal conversion competing with radiative decay (>1 ns).

Effects of Block Length in Copolymers Based on Regioregular Oligothiophenes Linked With Electron‐Accepting Units

Copolymers with an alternating structure of regioregular oligo(3-hexylthiophene) (O3HT) with different lengths and 2,5-dibutyl-3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP) were synthesized through Stille coupling reaction. The light absorption of the copolymers can be rationally tuned to have a broad spectrum across the visible region by adjusting the length of O3HT. Organic solar cells fabricated with the copolymers and PCBM showed a broad photoresponse and a comparable efficiency to that of poly(3-hexylthiophene) (P3HT):PCBM cells. The external quantum efficiency and fluorescence spectra suggested that the intrachain energy transfer from the O3HT block to the vicinity of the DPP unit could limit the photovoltaic performance of the copolymers.

Measurement of interchain and intrachain exciton hopping barriers in luminescent polymer

The integrated photoluminescence intensity in thin films of ‘Super Yellow’ copolymer has been analyzed using a Mott-like temperature dependence. This has enabled us to observe contributions from two emission channels, indicative of exciton recombination proceeding from two distinct origins. At high temperature, interchain thermally activated exciton energy transfer and migration dominates, resulting in large scale quenching of the integrated emission intensity and hence the photoluminescence quantum yield. However, at relatively low temperature, an additional increase of the integrated emission intensity occurs. This new channel of emission has been attributed to recombination from excitons where intrachain exciton energy transfer between adjacent subunits of the copolymer backbone becomes hindered. The activation energy barriers that control both of these emission channels have been obtained and are correlated with chain backbone degrees of freedom.

Effect of Aggregation on the Photophysical Properties of Three Fluorene–Phenylene-Based Cationic Conjugated Polyelectrolytes

The effect of aggregation on the photophysical properties of three cationic poly{9,9-bis[N,N-(trimethylammonium)hexyl] fluorene-co-l,4-phenylene} polymers with average chain lengths of ∼6, 12, and 100 repeat units (PFP-NR3(6(I),12(Br),100(Br))) has been studied by steady-state and time-resolved fluorescence techniques. Conjugated polyelectrolytes are known to aggregate in solution and for these PFP-NR3 polymers this causes a decrease in the fluorescence quantum yield. The use of acetonitrile as a cosolvent leads to the breakup of aggregates of PFP-NR3 in water; for PFP-NR3(6(I)), this results in an ∼10-fold increase in fluorescence quantum yield, a ca. 2-fold increase in the molar extinction coefficient at 380 nm, and an increase in the emission lifetime, as compared with polymer behavior in water. Fluorescence anisotropy also decreases with increasing aggregation, and this is attributed to increased fluorescence depolarization by interchain energy transfer in aggregate PFP-NR3 clusters. Förster resonance energy transfer along the polymer chain is expected to be very fast, with a calculated FRET rate constant of 7.3 × 10(12) s(-1) and a Förster distance of 2.83 nm (cf. the polymer repeat unit separation of 0.840 nm) for PFP-NR3(100(Br)). The complex polymer excited-state decay kinetics in aggregated PFP-NR3 systems have been successfully modeled in terms of intrachain energy transfer via migration and trapping at interchain aggregate trap sites, with model parameters in good agreement with data from picosecond time-resolved studies and the calculated theoretical Förster energy-transfer rates.

Photophysical and electroluminescent properties of a Series of Monochromatic red-emitting europium-complexed nonconjugated copolymers based on diphenylphosphine oxide modified polyvinylcarbazole

Two novel copolymers P1 and P2 were prepared by using the polymerizable aryl phosphine oxide based Eu(TTA) 3VBCzDPO ( EuM) ( VBCzDPO = 3,6-bis(diphenyl-phosphoryl)-9-(4- vinylbenzyl)-9H-carbazole) and vinylcarbazole as the monomers with the compositions of 1:99 and 1:33, respectively. It is showed that the stronger coordinate ability of bidentate APO ligands facilitates the stability of the complex monomer during polymerization, and their beetling coordinate sites and adjustable structure efficiently reduce the steric effect of bulky EuM. Both of photoluminescent (PL) spectra in solution and solid of the copolymers exhibited improved emission from Eu 3+ ion. The high PL quantum yield (PL QY) in solid of 60% is realized. Further investigation indicates that for the intra-chain energy transfer VBCzDPO serves as the intermediate and bridge between PVK and Eu(TTA) 3, which ensures the high efficiency of whole intra-chain energy transfer. The pure-red emission from the devices of P1 and P2 was demonstrated.

Electrothermal Manipulation of Individual Chromophores in Single Conjugated Polymer Chains: Controlling Intrachain FRET, Blinking, and Spectral Diffusion

Single molecule spectroscopy of individual chains of a conjugated polymer opens up deep insight into electronic localization phenomena, which govern the underlying optical properties of these complex and disordered materials. We explore the nature of a single chromophore arising in a delocalized pi-electron system by applying periodic electrothermal perturbations at low temperatures. Brief heating of the chromophore leads to a dramatic increase in the transition line width and is generally accompanied by a random jump of the emission energy. This observation demonstrates that chromophores on a polymer chain are not only defined by structural disorder but also by the subtleties of the local dielectric environment. The effect of thermal perturbation becomes more complex when long polymer chains are considered, which can potentially support the formation of multiple chromophores. Here, a momentary increase in temperature can promote intrachain energy transfer to quenching sites, leading to a strong modulation of emission intensity with temperature. Unexpectedly, such energy transfer can serve to either raise or lower the transition line width and quantum yield of the ensemble with increasing temperature, depending on the specific energetics of the chromophores in the system, which in turn vary with time. The controlled perturbation of both the emission spectrum and the intensity by brief heating of the polymer chain offers insight into possible microscopic origins of fluorescence blinking and spectral diffusion, which ultimately impact on the efficiency and spectral purity of devices.

Blue electroluminescence from 3,6‐silafluorene‐based copolymers

AbstractPoly(3,6‐silafluorene) is a typical wide band‐gap conjugated polymer with ultraviolet light emission. The blue electroluminescence from the 3,6‐silafluorene‐based copolymers via intrachain energy transfer was reported in this study. The monomer containing vinylene, anthracene, and tri‐arylamine moieties incorporated into the poly(3,6‐silafluorene) backbone can form efficient deep‐blue emitting copolymers with EL efficiency of 1.1–1.9%. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3286–3295, 2009

Electronic and Vibrational Coherences in Resonance Energy Transfer along MEH-PPV Chains at Room Temperature

In this work we report a study of the role of coherence dynamics in the intermediate coupling regime of electronic energy transfer (EET). Starting from the idea that in the intermediate coupling regime the phase information should be partially retained in a transfer process from a donor to an acceptor, we designed a new ultrafast experiment based on anisotropy decay along two time axes, capable of probing the degree of coherence characterizing this transfer. Conjugated polymer (poly[2-methoxy-5-(2'-ethyl-hexoxy)-1,4-phenylenevinylene], MEH-PPV) samples with different chain conformations were examined as a model multichromophoric system. The data, recorded at room temperature, reveal coherent transfer associated with intrachain energy transfer. These results were extended using two-dimensional photon echo measurements, which revealed the presence of long-lived intrachain electronic and vibrational coherences. Our results suggest that, in the intermediate coupling regime, quantum transport effects can occur when chemical bonds connecting donor and acceptor help to correlate their energy gap fluctuations. Moreover, they influence the mechanism of EET, even at room temperature.

Decoupling 2D Inter‐ and Intrachain Energy Transfer in Conjugated Polymers

The dimensionality of conjugated polymer systems plays an important role in energy-transfer processes, and 1D and 2D energy transfer of excitations are typically much slower than that between pi-stacked chains within a 3D polymeric solid. However, whether 2D energy transfer in conjugated polymers occurs mainly along polymer chains (intrachain), or between in-plain-adjacent polymer chains (interchain), has yet to be determined due to the difficulty of experimentally decoupling inter- and intrachain interaction in a 2D polymer system. This can be achieved by incorporating conjugated polymer chains into the planar galleries of layered matrices which sterically hinder polymer aggregation and pi-pi interchain interactions. Here, pristine blue-emitting polyfluorene chains and polyfluorene chains with known concentrations of green-emitting on-chain fluorenone defects are either separately or collectively incorporated into layered SnS(2). X-ray powder diffraction of the composite films confirms incorporation of the polymer chains into the layered galleries. Monitoring the fluorene-to-fluorenone energy transfer as a function of fluorenone concentration and distribution in the layered galleries allows differentiation between inter- and intrachain fluorene-fluorenone energy transfer. It is found that, 2D energy transfer in conjugated polymers follows mainly an interchain process, despite the absence of pi-pi interchain interactions.