Layer-by-Layer Assembled Films of Perylene Diimide- and Squaraine-Containing Metal–Organic Framework-like Materials: Solar Energy Capture and Directional Energy Transfer

Park, Hea Jung; So, Monica C.; Gosztola, David J.; Wiederrecht, Gary P.; Emery, Jonathan D.; Martinson, Alex B. F.; Er, Süleyman; Wilmer, Christopher E.; Vermeulen, Nicolaas A.; Aspuru‐Guzik, Alán; Farha, Omar K.; Hupp, Joseph T.

doi:10.1021/acsami.6b03307

Cited by 44 publications

(36 citation statements)

References 28 publications

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“…Note that the angle α represents the angle between the surface normal and the transition dipole moment and the orientation between this transition dipole and the molecule defines the final molecular orientation. In first approximation, we can consider that the transition dipole direction might coincide with the long molecular axis of the three PDI redox derivatives, which can be supported by the trend of the normalized absorbance variations observed in Figure b. Even if each redox specie has its own tilt angle, we assume that these three angles are very close.…”

Section: Resultsmentioning

confidence: 68%

Absorption Spectroelectrochemistry on Mixed Perylenediimide‐Based Self‐Assembled Monolayers: Non‐Linear Dependence of Absorbance versus Surface Coverage

et al. 2017

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The study of mixed self‐assembled monolayers of perylenediimide and hexanethiol by cyclic voltammetry and absorption spectroelectrochemistry shows a non‐linearity of absorbance maxima as a function of the surface coverage. This surprising result could be supported by an increase in the average tilt angle at low coverage, suggesting that the dilution of redox species through an alkanethiol would induce a change of the orientation of immobilized chromophores and, therefore, a modification of the optical properties of the monolayer.

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Section: Resultsmentioning

confidence: 68%

Absorption Spectroelectrochemistry on Mixed Perylenediimide‐Based Self‐Assembled Monolayers: Non‐Linear Dependence of Absorbance versus Surface Coverage

et al. 2017

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“…This issue was addressed in the earlier example of anisotropic energy transport in a Zn‐ADB MOF thin film . In this regard, Hupp and co‐workers also provided a strategy to guide excitation energy in a unidirectional fashion . They used a pillared‐layer Zn‐MOF type structure, in which the pillars (pyridyl end group) are perylenediimides (PDIs), and this structure is epitaxially grown on a substrate such that the PDIs are assembled orthogonal to the substrate plane (the orientation was investigated by polarization‐dependent absorption).…”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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In recent years, a particularly attractive and novel strategy has become available for the fabrication of photoresponsive, porous, and crystalline molecular solids from appropriately functionalized chromophoric linkers. The crystallinity of these materials allows a rather straightforward description and analysis using theoretical methods, thus tremendously accelerating the design of novel materials. This new class of crystalline molecular solids is referred to as metal-organic frameworks, MOFs (or porous coordination polymers, PCPs). [1] MOFs are constructed from metal-/metal-oxo nodes and organic linkers (Figure 1). The incorporation of photoactive species into MOFs may be realized by using them as linkers (method L) or attaching them to a linker (method A), as shown in Figure 1a. In addition, the porosity of MOFs allows the loading of chromophoric compounds as guests (method G) into the pores of this interesting framework material.In this review article, we mainly focus on organic photoactive species, which are either simply loaded as guests into porous MOFs or used after appropriate functionalization as building blocks for the construction of the framework (methods L, A, and G). [2] It is important to note that in the context of photoresponsive behavior, MOFs carry a potential which by far exceeds that of nonporous coordination polymers. This is because simple loading of guest/solvent molecules of different size/polarity/functionality in the MOF pores can impart a large optical response, which is useful, e.g., for sensing applications. [3] As an example, the solvent-dependent optical response or solvatochromism [4] is illustrated in Figure 1b. Such effects cannot be realized for nonporous coordination polymers.The different types of photoresponsive molecules addressed in this review can be grouped into two classes. The first contains molecules where the structure remains essentially unchanged upon light-induced electronic excitation, and the second contains molecular species that change their structure or conformation upon absorption of photons (molecular switches).Light with a wavelength in the range 200-800 nm (6.2-1.5 eV) can excite a molecule to a transient excited electronic state. The transient state then decays to a low-energy state, either the parent ground state or another longer-lived excited state. Decay time scales are in the range 10 −12 -10 1 s, and the released energy can be radiative or nonradiative in nature. For many applications, nonradiative energy loss is unwanted, When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well-defined structure carry substantial advantages over amorphous materials. Here, the metal-organic framework (MOF)-based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coo...

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“…Nevertheless, optimizing the transfer of energy within chromophore assemblies to the reaction center is equally important. The transport or diffusion of the exciton (the excited-state carrying the energy added to the molecule by the absorption of a photon) between chromophores depends on the architecture of the assembled chromophores 2 – 5 . Numerous studies have demonstrated that exciton motion in self-assembled organic molecular systems, conjugated polymers, nanostructures and organic–inorganic hybrid structures, critically depends on mesoscale order 6 – 8 .…”

Section: Introductionmentioning

confidence: 99%

Anisotropic energy transfer in crystalline chromophore assemblies

et al. 2018

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An ideal material for photon harvesting must allow control of the exciton diffusion length and directionality. This is necessary in order to guide excitons to a reaction center, where their energy can drive a desired process. To reach this goal both of the following are required; short- and long-range structural order in the material and a detailed understanding of the excitonic transport. Here we present a strategy to realize crystalline chromophore assemblies with bespoke architecture. We demonstrate this approach by assembling anthracene dibenzoic acid chromophore into a highly anisotropic, crystalline structure using a layer-by-layer process. We observe two different types of photoexcited states; one monomer-related, the other excimer-related. By incorporating energy-accepting chromophores in this crystalline assembly at different positions, we demonstrate the highly anisotropic motion of the excimer-related state along the [010] direction of the chromophore assembly. In contrast, this anisotropic effect is inefficient for the monomer-related excited state.

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Layer-by-Layer Assembled Films of Perylene Diimide- and Squaraine-Containing Metal–Organic Framework-like Materials: Solar Energy Capture and Directional Energy Transfer

Cited by 44 publications

References 28 publications

Absorption Spectroelectrochemistry on Mixed Perylenediimide‐Based Self‐Assembled Monolayers: Non‐Linear Dependence of Absorbance versus Surface Coverage

Absorption Spectroelectrochemistry on Mixed Perylenediimide‐Based Self‐Assembled Monolayers: Non‐Linear Dependence of Absorbance versus Surface Coverage

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Anisotropic energy transfer in crystalline chromophore assemblies

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