Photochemical Creation of Covalent Organic 2D Monolayer Objects in Defined Shapes <i>via</i> a Lithographic 2D Polymerization

Servalli, Marco; Çelebi, Kemal; Payamyar, Payam; Zheng, Li-Qing; Položij, Miroslav; Löwe, Benjamin; Kuc, Agnieszka; Schwarz, Tobias; Thorwarth, Kerstin; Borgschulte, Andreas; Heine, Thomas; Zenobi, Renato; Schlüter, A. Dieter

doi:10.1021/acsnano.8b05964

Cited by 19 publications

(16 citation statements)

References 57 publications

(90 reference statements)

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“…London dispersion interactions are commonly treated using an a posteriori correction [136,137] or the manybody dispersion (MBD) approach. [138] DFTB2 has been successfully applied to 2D COFs, [27,59,78,[139][140][141][142][143][144][145][146][147][148][149][150][151][152] DFTB3 has not yet been tested carefully with SOC and with periodic boundary conditions. Popular codes covering MOFs and COFs in periodic boundary conditions are dftb+ [153] and AMS/DFTB.…”

Section: Methodsmentioning

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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Section: Methodsmentioning

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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“…The sheet edges of the objects created are not sharp on a molecular scale, though, because light cannot be applied with nm‐precision. Shape creation has been used for writing and lithographic experiments and, in principle, is a way to store information. Writing in this context means to convert a monomer monolayer into a 2D polymer, whereby the process is read out by the fact that the monomer array fluoresces, while the polymer molecule obtained does not.…”

Section: Where the Field Might Gomentioning

confidence: 99%

Synthetic 2D Polymers: A Critical Perspective and a Look into the Future

Wang

Schlüter

2018

Macromol. Rapid Commun.

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structural order, in short: 2D polymers, and that the past is thus well taken care of.When talking about 2D polymers it is important to note that we use the term "polymer" in Staudinger's sense, that is, it is referring to a macromolecule whose structure, except for the end groups, can entirely be described by repeat units (RU). [4] This clause is important, as the term "2D polymer" had been used in various different meanings way before we proposed a definition in 2009. [2a] Examples include linear polymers confined to 2D space [5] as well as smectic liquid crystalline phases stabilized through linear polymerizations within the layers. [6] Though interesting in their own right, such macromolecules will not be considered in the current review article. When talking about synthetic 2D polymers, we refer to 2D polymers which can be synthesized under mild, typical organic chemistry-style conditions and not to 2D polymers including graphene [7] or (BN) x 2D PolymersThis feature article provides both a critical perspective as to where synthetic 2D polymers currently stand and a rather substantial view into how the future of this exciting field of polymer chemistry might look. It starts out by addressing strategic considerations meant to familiarize the reader with what to expect when entering the field. To better understand these considerations, the very nature of a 2D polymer is addressed in comparison to other organic 2D materials. Thereafter, the article moves quite intensely and critically into synthetic and mechanistic issues of 2D polymers before concentrating on the important structural analytics that one has to go through when unequivocally establishing these novel sheet-like polymeric objects. After a short excursion into the matter of exfoliation, the feature article then culminates in a section attempting to forecast the future. Key differences between 1D and 2D polymers are highlighted, and those considered by the authors to be the most attractive and burning research goals are further discussed. It is hoped that the reader will find this speculative section inspiring enough such that ideas that will help in advancing 2D polymers even faster are generated.

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“…London dispersion interactions are commonly treated using an a posteriori correction [138,139] or the many-body dispersion (MBD) approach. [140] DFTB2 has been successfully applied to 2D COFs, [27,59,78,[141][142][143][144][145][146][147][148][149][150][151][152][153][154] DFTB3 has not yet been tested carefully with SOC and with periodic boundary conditions. Popular codes covering MOFs and COFs in periodic boundary conditions are dftb+ [155] and AMS/DFTB.…”

Section: Dftbmentioning

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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Photochemical Creation of Covalent Organic 2D Monolayer Objects in Defined Shapes via a Lithographic 2D Polymerization

Cited by 19 publications

References 57 publications

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

Synthetic 2D Polymers: A Critical Perspective and a Look into the Future

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

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