Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities

Haldar, Ritesh; Fu, Zhaoming; Joseph, Reetu; Herrero, David; Martín‐Gomis, Luis; Richards, Bryce S.; Howard, Ian A.; Sastre‐Santos, Ángela; Wöll, Christof

doi:10.1039/d0sc02436h

Cited by 20 publications

(31 citation statements)

References 47 publications

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“…For example, the flexible and easy-processing nature of organic semiconductors may allow various materials to exhibit exciton-photon coupling and bring novel application possibilities. [166,167] The fruitful excited-state processes in organic materials may be further modified by the existence of coherent polariton condensates. More diverse polariton devices can be developed by enhancing the nonlinear polariton interactions, harnessing the anisotropy and introducing the spin degree of freedom.…”

Section: Discussionmentioning

confidence: 99%

Exciton‐Polaritons and Their Bose–Einstein Condensates in Organic Semiconductor Microcavities

et al. 2021

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Exciton‐polaritons are half‐light, half‐matter bosonic quasiparticles formed by strong exciton–photon coupling in semiconductor microcavities. These hybrid particles possess the strong nonlinear interactions of excitons and keep most of the characteristics of the underlying photons. As bosons, above a threshold density they can undergo Bose–Einstein condensation to a polariton condensate phase and exhibit a rich variety of exotic macroscopic quantum phenomena in solids. Recently, organic semiconductors have been considered as a promising material platform for these studies due to their room‐temperature stability, good processability, and abundant photophysics and photochemistry. Herein, recent advances of exciton‐polaritons and their Bose–Einstein condensates in organic semiconductor microcavities are summarized. First, the basic physics is introduced, and then their emerging applications are highlighted. The remaining questions are also discussed and a personal viewpoint about the potential directions for future research is given.

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Section: Discussionmentioning

confidence: 99%

Exciton‐Polaritons and Their Bose–Einstein Condensates in Organic Semiconductor Microcavities

et al. 2021

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“…Such high optical quality MOF thin films were successfully used for photon upconversion, [30] highly anisotropic directional transport of excitons, [31] J-aggregate formation, [32] and as an active medium in optical cavities. [33,34] Considering the requirements listed above for fabricating energy conversion cascades, it seems straightforward to follow the scheme depicted in Figure 1a to realize trilayer systems of chromophoric SURMOFs, since lbl methods are well suited to the fabrication of a hetero-multilayer. [35] A particular advantage of chromophoric SURMOFs is the crystallinity and high degree of orientation of these thin films, resulting in very high absorption efficiency [36] and the emergence of long-range anisotropic FRET transfer.…”

Section: Introductionmentioning

confidence: 99%

“…Such high optical quality MOF thin films were successfully used for photon upconversion, [ 30 ] highly anisotropic directional transport of excitons, [ 31 ] J‐aggregate formation, [ 32 ] and as an active medium in optical cavities. [ 33,34 ]…”

Section: Introductionmentioning

confidence: 99%

Antenna Doping: The Key for Achieving Efficient Optical Wavelength Conversion in Crystalline Chromophoric Heterolayers

Haldar

Chen

Mazel

et al. 2021

Adv Materials Inter

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For efficient light absorption, a huge variety of dyes is available, both from nature [2] as well as from organic synthesis, with many of them relying on extended π-conjugated structures. [3,4] To avoid reemission, the energy stored in the form of electronic excitations must be transported to regions in space where it can be converted into another form of energy, either chemical or electrical. In mesoscale assemblies, this exciton transport [5] is often inefficient, since abundant unwanted interchromophore interactions lead to nonradiative deactivation or fluorescence quenching. Some of the commonly encountered loss processes result from H-type aggregate formation, structural defects, unwanted electron transfer (charge separation), etc. [6,7] In order to avoid such losses upon energy transfer, high-purity and structurally perfect structures are required. Furthermore, established device architectures require a directional transport of excitons, as isotropic processes will greatly reduce device performance. [8] The most efficient transfer mechanism for singlet excitons is Förster resonance energy transfer (FRET). This mechanism allows the straightforward realization of a wavelength converter together with directional energy transport by arranging suitable donor-acceptor (D-A) pairs into a chain, e.g., consisting of three different chromophores C1, C2, and C3 as illustrated in Figure 1a. If the emission of C1 and the absorption of C2, as well as the emission of C2 and the absorption of C3, show sufficient spectral overlap, efficient FRET will cause the trimer to function as a two-step cascade in which the directed energy conversion of photons is absorbed in C1 via C2 to C3 (Figure 1a,b).On the molecular level, a variety of organic synthesis schemes for the fabrication of such cascades have been reported, with most of them based on sophisticated coupling chemistry using suitable building blocks. [9] However, for integration into organic photovoltaic (OPV) devices, mesoscopic assemblies providing transport on a macroscopic scale are mandatory. [10] While a number of approaches have been presented to fabricate such chromophoric aggregates, e.g., based on zeolites, [11] solvated molecules, gels (randomly oriented), or dendritic systems, [12][13][14][15][16] only a few of these strategies are compatible with contemporary OPV device architectures. Moreover, most of these previously High-yield wavelength conversion is one of the key requirements for efficient photon energy harvesting. Attempts to realize efficient conversion by simply stacking layers of chromophores have failed so far, even when using highly crystalline assemblies and employing the recently discovered long-range (>100 nm) Förster resonance energy transfer (LR-FRET). Optical conversion efficiency is drastically improved using chromophoric metal-organic framework heterolayers fabricated layer-by-layer in connection with an "antenna doping" strategy. Systematic investigations reveal that the LR-FRET mechanism, reported previously in chromophoric aggregates, i...

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“…The huge variety of conceivable nodes and linkers has led to the synthesis of tens of thousands of different systems with specifically tuned properties [ 2 ]. Besides their established applications in areas like catalysis [ 3 , 4 , 5 ] gas storage [ 6 , 7 , 8 ] and gas separation [ 9 , 10 ] in recent years also their electronic and optical properties have attracted considerable interest [ 11 , 12 , 13 , 14 , 15 ]. Chromophores incorporated into MOFs have already been explored in sensing [ 16 , 17 ] and artificial light harvesting [ 18 , 19 , 20 ].…”

Section: Introductionmentioning

confidence: 99%

Exciton Coupling and Conformational Changes Impacting the Excited State Properties of Metal Organic Frameworks

et al. 2020

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In recent years, the photophysical properties of crystalline metal-organic frameworks (MOFs) have become increasingly relevant for their potential application in light-emitting devices, photovoltaics, nonlinear optics and sensing. The availability of high-quality experimental data for such systems makes them ideally suited for a validation of quantum mechanical simulations, aiming at an in-depth atomistic understanding of photophysical phenomena. Here we present a computational DFT study of the absorption and emission characteristics of a Zn-based surface-anchored metal-organic framework (Zn-SURMOF-2) containing anthracenedibenzoic acid (ADB) as linker. Combining band-structure and cluster-based simulations on ADB chromophores in various conformations and aggregation states, we are able to provide a detailed explanation of the experimentally observed photophysical properties of Zn-ADB SURMOF-2: The unexpected (weak) red-shift of the absorption maxima upon incorporating ADB chromophores into SURMOF-2 can be explained by a combination of excitonic coupling effects with conformational changes of the chromophores already in their ground state. As far as the unusually large red-shift of the emission of Zn-ADB SURMOF-2 is concerned, based on our simulations, we attribute it to a modification of the exciton coupling compared to conventional H-aggregates, which results from a relative slip of the centers of neighboring chromophores upon incorporation in Zn-ADB SURMOF-2.

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Guest-responsive polaritons in a porous framework: chromophoric sponges in optical QED cavities

Abstract: Introducing porous material into optical cavities is a critical step toward the utilization of quantum-electrodynamical (QED) effects for advanced technologies, e.g. in the context of sensing. We demonstrate that crystalline,...

Cited by 20 publications

References 47 publications

Exciton‐Polaritons and Their Bose–Einstein Condensates in Organic Semiconductor Microcavities

Exciton‐Polaritons and Their Bose–Einstein Condensates in Organic Semiconductor Microcavities

Antenna Doping: The Key for Achieving Efficient Optical Wavelength Conversion in Crystalline Chromophoric Heterolayers

Exciton Coupling and Conformational Changes Impacting the Excited State Properties of Metal Organic Frameworks

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