A de novo strategy for predictive crystal engineering to tune excitonic coupling

Haldar, Ritesh; Mazel, Antoine; Krstić, Marjan; Zhang, Qiang; Jakoby, Marius; Howard, Ian A.; Richards, Bryce S.; Jung, Nicole; Jacquemin, Denis; Diring, Stéphane; Wenzel, Wolfgang; Odobel, Fabrice; Wöll, Christof

doi:10.1038/s41467-019-10011-8

Cited by 53 publications

(69 citation statements)

References 66 publications

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“…This was the first case where crystal structure prediction (CSP) was employed to tune the photophysical properties of a chromophoric MOF material. When the first cNDI linker was assembled to yield the corresponding SURMOF, the resulting chromophoric assembly was dark, that is, a so‐called H‐aggregate was realized 53a. A computational analysis confirmed the existence of a parallel arrangement of the corresponding transition dipole moments, where the photoexcitation energy decays nonradiatively due to forbidden electronic transition 53b.…”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 93%

“…Another very interesting class of highly fluorescent chromophores, core‐substituted naphthalenediimide (cNDI), can also be deposited as MOF thin films . This was the first case where crystal structure prediction (CSP) was employed to tune the photophysical properties of a chromophoric MOF material.…”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

“…When the first cNDI linker was assembled to yield the corresponding SURMOF, the resulting chromophoric assembly was dark, that is, a so‐called H‐aggregate was realized 53a. A computational analysis confirmed the existence of a parallel arrangement of the corresponding transition dipole moments, where the photoexcitation energy decays nonradiatively due to forbidden electronic transition 53b. Since the goal was to realize a J‐aggregate with bright, long‐lived fluorescence having large delocalization of excitation energy, the chemical structure of the cNDI linker was slightly modified by attaching a so‐called steric control unit (SCU).…”

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

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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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Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 93%

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

Section: Short‐lived Photoexcited State Of Chromophoresmentioning

confidence: 99%

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Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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“…As demonstrated in recent work, when restricting the size of these units to values smaller than the MOF pore size, the packing of aromatic moieties within the MOF linkers can be varied without changing overall lattice parameters of the MOF material. [115] In particular, by first creating libraries in silico using appropriate computational workflows (as described in refs. [115,116]), [7] at the DFT/PBE0-D3 level of theory with all electron basis set (double zeta with polarization on light elements and triple zeta with polarization for Cu atoms) as implemented in Crystal14.…”

Section: Proximity Effect In Metal-organic Framework: the Surmof Shomentioning

confidence: 99%

Proximity Effect in Crystalline Framework Materials: Stacking‐Induced Functionality in MOFs and COFs

Kuc

Springer

Batra

et al. 2020

Adv Funct Materials

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Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) consist of molecular building blocks being stitched together by strong bonds. They are well known for their porosity, large surface area, and related properties. The electronic properties of most MOFs and COFs are the superposition of those of their constituting building blocks. If crystalline, however, solid-state phenomena can be observed, such as electrical conductivity, substantial dispersion of electronic bands, broadened absorption bands, formation of excimer states, mobile charge carriers, and indirect band gaps. These effects emerge often by the proximity effect caused by van der Waals interactions between stacked aromatic building blocks. Herein, it is shown how functionality is imposed by this proximity effect, that is, by stacking aromatic molecules in such a way that extraordinary properties emerge in MOFs and COFs. After discussing the proximity effect in graphene-related materials, its importance for layered COFs and MOFs is shown. For MOFs with well-defined structure, the stacks of aromatic building blocks can be controlled via varying MOF topology, lattice constant, and by attaching steric control units. Finally, an overview of theoretical methods to predict and analyze these effects is given, before the layer-by-layer growth technique for well-ordered surface-mounted MOFs is summarized.

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“…As demonstrated in recent work, when restricting the size of these units to values smaller than the MOF pore size, the packing of aromatic moieties within the MOF linkers can be varied without changing overall lattice parameters of the MOF material. [117] In particular, by first creating libraries in-silico using appropriate computational workflows (as described in [117,118] ), the structures of interest can be identified by computational screening of large libraries, before linkers equipped with the "best" SCU are synthesized and used to assemble the corresponding MOFs or SURMOFs. Additionally, the individual MOF layers provide strong anisotropic transport properties for excitons and other optical excitations.…”

Section: Proximity Effect In Metal-organic Framework: the Surmof Shomentioning

confidence: 99%

Proximity Effect in Crystalline Framework Materials: Stacking-Induced Functionality in MOFs and COFs

Kuc¹,

Springer²,

Batra³

et al. 2019

Preprint

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<div>Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) consist of molecular building blocks being stitched together by strong bonds. They are well known for their porosity, large surface area, and related properties. The electronic properties of most MOFs and COFs are the superposition of those of their constituting building blocks. If crystalline, however, solid-state phenomena can be observed, such as electrical conductivity, substantial dispersion of electronic bands, broadened absorption bands, formation of excimer states, mobile charge carriers, and indirect band gaps. These effects emerge often by the proximity effect caused by the van-der-Waals interactions between stacked aromatic building blocks. This Progress Report shows how functionality is imposed by this proximity effect, that is, by stacking aromatic molecules in such a way that extraordinary electronic and optoelectronic properties emerge in MOFs and COFs. After discussing the proximity effect in graphene-related materials, its importance for layered COFs and MOFs is shown. For MOFs with well-defined structure, the stacks of aromatic building blocks can be controlled via varying MOF topology, lattice constant, and by attaching steric control units. Finally, an overview of theoretical methods to predict and analyze these effects is given, before the layer-by-layer growth technique for well-ordered surface-mounted MOFs is summarized.</div>

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A de novo strategy for predictive crystal engineering to tune excitonic coupling

Cited by 53 publications

References 66 publications

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Proximity Effect in Crystalline Framework Materials: Stacking‐Induced Functionality in MOFs and COFs

Proximity Effect in Crystalline Framework Materials: Stacking-Induced Functionality in MOFs and COFs

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