Controlling Multiphoton Absorption Efficiency by Chromophore Packing in Metal–Organic Frameworks

Mayer, David C.; Manzi, Aurora; Medishetty, Raghavender; Winkler, Benedikt; Schneider, Christian; Kieslich, Gregor; Pöthig, Alexander; Feldmann, Jochen; Fischer, Roland A.

doi:10.1021/jacs.9b04213

Cited by 65 publications

(62 citation statements)

References 82 publications

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“…Results collected thus far are highly promising, as they demonstrate that CPs and MOFs offer very good NLO responses, which are sufficiently high to realize photonic applications, for example two-photon pumped lasing [47] or non-contact luminescence thermometry mediated by three-photon absorption [48]. From the fundamental science point of view, it also emerged that the solid state, aggregated nature of those compounds itself creates new pathways for the enhancement of nonlinear absorption [49]. One of the postulated mechanisms that are seen responsible for enhanced NLO properties of CPs is the aggregation of aromatic ligands and the conformational strain connected with this [46].…”

Section: Introductionmentioning

confidence: 99%

Nonlinear Optical Pigments. Two-Photon Absorption in Crosslinked Conjugated Polymers and Prospects for Remote Nonlinear Optical Thermometry

2020

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Nonlinear optical (NLO) pigments are compounds insoluble in solvents that exhibit phenomena related to nonlinear optical susceptibilities (χ(n) where n = 2,3,...), e.g., two-photon absorption (2PA) which is related to the imaginary part of χ(3). Determination of spectrally-resolved 2PA properties for NLO pigments of macromolecular nature, such as coordination polymers or crosslinked polymers, has long been a challenging issue due to their particulate form, precluding characterizations with standard techniques such as Z-scan. In this contribution, we investigate thus far unknown spectrally-resolved 2PA properties of a new subclass of NLO pigments—crosslinked conjugated polymers. The studied compounds are built up from electron-donating (triphenylamine) and electron-withdrawing (2,2’-bipyridine) structural fragments joined by vinylene (Pol1) or vinyl(4-ethynylphenyl) (Pol2) aromatic bridges. 2PA properties of these polymers have been characterized in broad spectral range by specially modified two-photon excited fluorescence (TPEF) techniques: solid state TPEF (SSTPEF) and internal standard TPEF (ISTPEF). The impact of self-aggregation of aromatic backbones on the 2PA properties of the polymers has been evaluated through extended comparisons of NLO parameters, i.e., 2PA cross sections (σ2) and molar-mass normalized 2PA merit factors (σ2/M) with those of small-molecular model compounds: Mod1 and Mod2. By doing this, we found that the 2PA response of Pol1 and Pol2 is improved 2–3 times versus respective model compounds in the solid state form. Further comparisons with 2PA results collected for diluted solutions of Mod1 and Mod2 supports the notion that self-aggregated structure contributes to the observed enhancement of 2PA response. On the other hand, it is clear that Pol1 and Pol2 suffer from aggregation-caused quenching phenomenon, well reflected in time-resolved fluorescence properties as well as in relatively low values of quantum yield of fluorescence. Accordingly, despite improved intrinsic 2PA response, the effective intensity of two-photon excited emission for Pol1 and Pol2 is slightly lower relative to Mod1 and Mod2. Finally, we explore temperature-resolved luminescence properties under one- (377 nm), two- (820 nm), and three-photon excitation (1020 nm) conditions of postsynthetically Eu3+-functionalized material, Pol1-Eu, and discuss its suitability for temperature sensing applications.

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Section: Introductionmentioning

confidence: 99%

Nonlinear Optical Pigments. Two-Photon Absorption in Crosslinked Conjugated Polymers and Prospects for Remote Nonlinear Optical Thermometry

2020

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“…[153] They further derived structure-property relations of the interplay between the photonic properties and the spatial arrangements of optically active chromophores within the framework. [154] The TPA-induced photoluminescence properties of two MOFs based on a D-A tetraphenylphenylenediamine (tPPD) chromophore linker (H 4 TPBD) were investigated. The enhancement of the structure related relative TPA cross-section is likely due to the enhanced "through-space" interaction in materials caused by the tighter and special arrangement of chromophores.…”

Section: Organic/inorganic Hybrid Porous Materials For Third-order Nlomentioning

confidence: 99%

Crystalline Porous Materials for Nonlinear Optics

Shi

Han

et al. 2021

Small

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metal chalcogenides, [17,18] graphdiyne, [19][20][21] etc.) and perovskites [22][23][24][25][26] have been in a state of vigorous development and rapid advances for applications in optoelectronics, catalysis, energy conversion, due to their autologous admirable chemistry and physics characteristics. [27,28] Porous materials, a scientifically evolving and functionally compelling class of solid compounds with well-defined pore structures, such as metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and polyoxometalates (POMs), have attracted broad research interest because of their wide applications in many fields including, but not limited to, adsorption, separation, catalysis, and photovoltaics. [29][30][31][32] Through fine control over the organic units to create predesigned skeletons, an exceptionally large set of materials with unique porous structures and remarkable properties have been developed. [33,34] MOFs, also known as coordination polymers or coordination networks, are one class of crystalline porous materials prepared by the self-assembly of metal ions or clusters with organic ligands. [35] They have drawn tremendous research interest for their customizable chemical structures along with unique chemical and physical properties, [36][37][38][39][40][41] which guarantee their wide applications as adsorption and separation, catalysts, magnetic, and light emitting materials. [36,[42][43][44][45] The use of appropriate ligands with optimized electronic push-pull structures, the degree of conjugation in the system and the encapsulation of guest molecules with different properties are some of the effective strategies to enhance the linear and nonlinear optical properties of the MOFs materials. [46][47][48] COFs, constructed from organic moltifs linking through strong covalent bonding, are a kind of crystalline porous materials in which the atoms of organic units are precisely integrated to create periodic frameworks and nanopores. [49,50] Although the thermal stability and crystallinity of COFs are lower than MOFs, they have received wide attention due to their low density, large surface area and strong ππ stacking. [51][52][53][54] It has been appreciated that the applications of COFs materials in third-order NLO such as two-photon fluorescence have been well developed in recent years. [55][56][57] Similar to MOFs and COFs, POMs formed by the coordination of early transition metals and oxygen atoms are a class of crystalline porous materials with unique structures and properties for their exceptional crystallinity and high stability. [58] POMs are intrinsically electron deficient, and their electronaccepting capability in combination with highly delocalized π-conjugated systems is particularly promising for producing NLO materials. [59,60] The structure of all the crystalline porous Crystalline porous materials have been extensively explored for wide applications in many fields including nonlinear optics (NLO) for frequency doubling, two-photon absorption/emission, optical limiting effect,...

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“…This issue was first addressed by Fischer and co-workers who investigated two MOFs based on a push-pull chromophore, tetrakis(1,1′biphenyl-4-carboxylic acid)-1,4-benzenediamine (TPPD), and Cd 2+ (tPPD-Cd) and Zn 2+ (tPPD-Zn) ions. [33] In both cases, the crystal packing can be described as being of the "herringbone" type, but these MOFs differ in terms of dimensionality and topology of their coordination nets; while tPPD-Cd is a threefold interpenetrated net of the cds topological type, tPPD-Zn is a 2D CPs described by twofold interpenetrated sql net. 2PA cross sections of tPPD-Cd and tPPD-Zn have been measured with the use of the SSTPEF method.…”

Section: Impact Of Coordination Net Topology On 2pa Properties Of Mofsmentioning

confidence: 99%

Nonlinear Optical Properties of Emerging Nano‐ and Microcrystalline Materials

Zarȩba

Nyk

Samoć

2021

Advanced Optical Materials

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The activity in the research on novel optical materials exhibiting nonlinear optical (NLO) properties is surveyed, especially nonlinear absorption, that may be attractive for various applications, including those in optoelectronics, photonics, and biophotonics. The recently introduced concept of “NLO pigments”—insoluble colored materials that can exhibit useful NLO effects—is demonstrated to apply to the multifunctional group of coordination polymers (CPs) and their subgroup of metal‐organic frameworks (MOFs), which may be applied in their microcrystalline form or as nanoparticles. Nanocrystalline materials such as semiconductor quantum dots or plasmonic particles made of noble metals have been widely studied and their properties have been often reviewed, thus they are not included in this review. On the other hand, studies performed on perovskites are described: materials that appear to have great potential for NLO applications in addition to their well‐known merit in photovoltaics. There is also much activity in the field of low‐dimensional, especially 2D structures of various kinds, and this review covers many examples of such structures, not including the broad topic of carbon nanostructures (graphene, nanotubes etc.) but concentrating on other emerging nonlinear optical materials such as black phosphorus, transition metal dichalcogenides, MXenes, and topological insulators.

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Controlling Multiphoton Absorption Efficiency by Chromophore Packing in Metal–Organic Frameworks

Cited by 65 publications

References 82 publications

Nonlinear Optical Pigments. Two-Photon Absorption in Crosslinked Conjugated Polymers and Prospects for Remote Nonlinear Optical Thermometry

Nonlinear Optical Pigments. Two-Photon Absorption in Crosslinked Conjugated Polymers and Prospects for Remote Nonlinear Optical Thermometry

Crystalline Porous Materials for Nonlinear Optics

Nonlinear Optical Properties of Emerging Nano‐ and Microcrystalline Materials

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