Understanding Self-Assembly of Porphyrin-Based SURMOFs: How Layered Minerals Can Be Useful

Meshkov, Ivan N.; Zvyagina, Alexandra I.; Shiryaev, A. A.; Nickolsky, Maximilian S.; Baranchikov, А. Е.; Ezhov, A. A.; Nugmanova, Alsu G.; Enakieva, Yu. Yu.; Gorbunova, Yulia G.; Arslanov, V. V.; Kalinina, Maria A.

doi:10.1021/acs.langmuir.7b04384

Cited by 22 publications

(15 citation statements)

References 45 publications

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“…The availability of functional rGO frameworks, which can combine micro‐, meso‐ and macropores on a scale ranging from Ångstrom to micrometres, remains rare . Access to such materials is, to date, rather scarce . Their micro‐ and meso‐porosities endow high specific surface areas, while the macroporosity guarantees accessibility to this surface and renders their surface chemically reactive in a variety of applications.…”

Section: Introductionmentioning

confidence: 99%

Directed Molecular Stacking for Engineered Fluorescent Three‐Dimensional Reduced Graphene Oxide and Coronene Frameworks

Mao

Cortezon‐Tamarit

et al. 2019

ChemistryOpen

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Three-dimensional fluorescent graphene frameworks with controlled porous morphologies are of significant importance for practical applications reliant on controlled structural and electronic properties, such as organic electronics and photochemistry. Here we report a synthetically accessible approach concerning directed aromatic stacking interactions to give rise to new fluorogenic 3D frameworks with tuneable porosities achieved through molecular variations. The binding interactions between the graphene-like domains present in the in situ-formed reduced graphene oxide (rGO) with functional porphyrin molecules lead to new hybrids via an unprecedented solvothermal reaction. Functional free-base porphyrins featuring perfluorinated aryl groups or hexyl chains at their meso-and β-positions were employed in turn to act as directing entities for the assembly of new graphene-based and foam-like frameworks and of their corresponding coronene-based hybrids. Investigations in the dispersed phase and in thin-film by XPS, SEM and FLIM shed light onto the nature of the aromatic stacking within functional rGO frameworks (denoted rGOFs) which was then modelled semi-empirically and by DFT calculations. The pore sizes of the new emerging reduced graphene oxide hybrids are tuneable at the molecular level and mediated by the bonding forces with the functional porphyrins acting as the "molecular glue". Single crystal X-ray crystallography described the stacking of a perfluorinated porphyrin with coronene, which can be employed as a molecular model for understanding the local aromatic stacking order and charge transfer interactions within these rGOFs for the first time. This opens up a new route to controllable 3D framework morphologies and pore size from the Ångstrom to the micrometre scale. Theoretical modelling showed that the porosity of these materials is mainly due to the controlled inter-planar distance between the rGO, coronene or graphene sheets. The host-guest chemistry involves the porphyrins acting as guests held through π-π stacking, as demonstrated by XPS. The objective of this study is also to shed light into the fundamental localised electronic and energy transfer properties in these new molecularly engineered porous and fluorogenic architectures, aiming in turn to understand how functional porphyrins may exert stacking control over the notoriously disordered local structure present in porous reduced graphene oxide fragments. By tuning the porosity and the distance between the graphene sheets using aromatic stacking with porphyrins, it is also possible to tune the electronic structure of the final nanohybrid material, as indicated by FLIM experiments on thin films. Such nanohybrids with highly controlled pores dimensions and morphologies open the way to new design and assembly of storage devices and applications incorporating π-conjugated molecules and materials and their πstacks may be relevant towards selective separation membranes, water purification and biosensing applications.

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Section: Introductionmentioning

confidence: 99%

Directed Molecular Stacking for Engineered Fluorescent Three‐Dimensional Reduced Graphene Oxide and Coronene Frameworks

Mao

Cortezon‐Tamarit

et al. 2019

ChemistryOpen

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“…By exploiting hydrogen or/and coordination bonding, the epitaxial protocol can be applied for fabrication of the GO-based hybrids with a desirable thickness and composition including ordered assemblies of organic chromophores integrated with GO [33,34]. This method has already been used for producing highly ordered surface-anchored metal-organic frameworks (SURMOFs) from carboxyl-and pyridyl-substituted porphyrin and perylene derivatives on the GO monolayers [35,36]. The GO sublayer provides a smooth planar template, on which SURMOFs are formed via coordination bonding between the functional groups of GO and organic molecules mediated by metal clusters.…”

Section: Introductionmentioning

confidence: 99%

A tool-box strategy for layer-by-layer assembly of ultrathin hybrid films from graphene oxide and chromophores for organic electronics

Gusarova

Zvyagina

Aleksandrov

et al. 2022

Preprint

Self Cite

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A combinatorial interfacial assembly method was developed for fabrication functionally different 2D hybrids by using the same starting set of components comprising graphene oxide, perylene chromophore, polydiacetylene surfactant and nickel nitrate as a source of divalent ions. The components were assembled through either hydrogen or coordination bonding into layered nanofilms with a thickness 8-20 nm to integrate them into conventional ITO-based solar cells. Depending on their composition, the hybrids provide different operational characteristics to the resulting devices. The combination of graphene oxide with the light-absorbing polymer provides photovoltaic properties, whereas the adding of nickel transforms the hybrid into the monopolar conductive layers. The combination of two chromophores gives a multipurpose nanoelement, which performs as either non-linear resistor, diode or photodiode. This strategy can be easily extended to other combinations of chemical tools for the design of various hybrid nanofilms with desirable functional properties for organic electronics.

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“…14 And this understanding is even more limited on surfaces. [15][16][17][18][19][20] This lack of knowledge forces the optimization of the synthesis conditions to be only attained through tedious systematic screening. In this paper, we report the synthesis and first systematic study on the growth of Cu(2-fluorobenzene-1,4-dicarboxylic acid)(DABCO) 0.5 or F-DMOF-1(Cu) (Figure 1b) as thin films (< 100 nm).…”

Section: Introductionmentioning

confidence: 99%

“…For example, in 2016 the production of MOF-coated gas tanks allowed the storage of dangerous gases at subambient pressures (ION-X by NuMat), and a MOF containing sachet is now used to slowly release an antiripening molecule to store fruits and vegetables for longer times (TruPick by MOF Technologies). , Despite these few examples of SURMOFs as functional materials and the impressive list of MOFs reported in the literature, there is a relatively limited amount of theoretical and experimental understanding about their growth processes . And this understanding is even more limited on surfaces. − This lack of knowledge forces the optimization of the synthesis conditions to be only attained through tedious systematic screening.…”

Section: Introductionmentioning

confidence: 99%

Impact of Synthetic Conditions on the Morphology and Crystallinity of FDMOF-1(Cu) Thin Films

Lugier

Pokharel

Castellanos

2020

Crystal Growth & Design

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Metal-organic frameworks (MOFs) have attracted a lot of interest for their numerous properties. However they are usually obtained as a powder (bulk) or as single crystals, which complicates their implementation into devices that could further exploit these properties. The development of Surface Anchored MOFs (SURMOFs), allowed to synthesize MOFs' thin films chemisorbed to a substrate, creating a viable solution to the device integration problem. Yet, the fundamental understanding of the mechanisms governing their growth remains limited and the systematic optimization of synthetic parameters is tedious. More studies on SURMOFs growth are needed before MOFbased devices become the norm. In this paper, a pillared-layer MOF with fluorinated terephthalate linkers, Cu 2 (fbdc) 2 (dabco) or F-DMOF-1(Cu), was synthesized on functionalized gold surfaces using a layer-by-layer method of Liquid Phase Epitaxy (LPE). The effects of temperature, linker concentration, type of surface functionalization and sonication during the rinsing step on coverage, film morphology and crystal orientation were studied. We found that the concentration of the linker has a strong impact on the morphology of the crystallites formed as well as on the surface coverage. It was noticed that the crystalline orientation is not only governed by the functionalization of the substrate, supporting the hypothesis that SURMOF thin films can switch their crystalline orientation during growth. This study adds information on which variables affect the formation of the first layers of a prototypical SURMOF.

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Understanding Self-Assembly of Porphyrin-Based SURMOFs: How Layered Minerals Can Be Useful

Cited by 22 publications

References 45 publications

Directed Molecular Stacking for Engineered Fluorescent Three‐Dimensional Reduced Graphene Oxide and Coronene Frameworks

Directed Molecular Stacking for Engineered Fluorescent Three‐Dimensional Reduced Graphene Oxide and Coronene Frameworks

A tool-box strategy for layer-by-layer assembly of ultrathin hybrid films from graphene oxide and chromophores for organic electronics

Impact of Synthetic Conditions on the Morphology and Crystallinity of FDMOF-1(Cu) Thin Films

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