Layer-by-layer assembly of porphyrin-based metal–organic frameworks on solids decorated with graphene oxide

Zvyagina, Alexandra I.; Shiryaev, A. A.; Baranchikov, А. Е.; Чернышев, Владимир В.; Enakieva, Yu. Yu.; Raitman, Oleg A.; Ezhov, A. A.; Meshkov, Ivan N.; Grishanov, Dmitry A.; Иванова, О. С.; Gorbunova, Yulia G.; Arslanov, V. V.; Kalinina, Maria A.

doi:10.1039/c6nj03202h

Cited by 35 publications

(19 citation statements)

References 42 publications

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“…In this new 2D ZnTCPP SURMOF, [38][39][40] the paddle-wheel Zn 2 (COO) 4 metal nodes are connected by the tetratopic TCPP ligands, forming layers which are stacked perpendicular to the substrate in an AB packing fashion (Figure 1c,d). Note, that in this structure the PW units are located directly above the center of the macrocycles of the previous layer ( Figure 1c and Figure S1, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

van der Waals Epitaxial Growth of 2D Metal–Porphyrin Framework Derived Thin Films for Dye‐Sensitized Solar Cells

Wang

Chen

Haldar

et al. 2018

Adv Materials Inter

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nature, which cannot meet the increasing demand for its broad applications in DSSCs. Thus, there is a huge interest in Pt-free materials for CE fabrication, such as inorganic semiconductors, [5] carbon materials, [6] conductive organic polymers, [7] and so on. [8,9] Metal-organic frameworks (MOFs) represent a class of porous coordination polymers that consist of organic ligands linker by metal ions to form crystalline assemblies, [10,11] which have been widely investigated for their attractive physical and chemical properties. [12,13] Recently, the tunable functionality of MOFs has allowed these porous materials as precursors or sacrificial templates for the preparation of electrode materials in DSSCs. [14,15] In particular, porphyrin-based MOFs (also called metal-porphyrin frameworks) [16] have been demonstrated to exhibit tunable optical, electrical, and photophysical properties, [17][18][19] which in particular suggest applications in DSSCs. However, up to now, employing metal-porphyrin frameworks for CE materials in DSSCs has not been reported.When aiming to use the potential of MOFs for electrical, electrochemical, and electronic applications, MOF thin films [20][21][22] prepared by a layer-by-layer (lbl) liquid-phase epitaxial (LPE) procedure have attracted huge interest. These surfacemounted MOFs or SURMOFs are assembled by a sequence of simple immersion processes, subsequently into solution of the metal source and the organic ligand. They exhibit a number of interesting properties, including controllable thickness, crystallinity, high degree of orientation, and homogeneous surface. So far, the lbl-approach has been successfully used to realize several types of SURMOFs, [23] e.g., HKUST-1 (Cu 3 (BTC) 2 , BTC = benzene-1,3,5-tri-carboxylate), SURMOF-2, Zn(2-methylimidazolate) 2 (ZIF-8), etc. [23][24][25] These SUR-MOFs are epitaxially grown on appropriately functionalized substrates by coordination bonding between metal ions and organic ligands. The growth of SURMOFs based on lbl protocols involving noncovalent interactions (such as van der Waals, hydrogen bonding, and other weak interactions, etc.) has not yet been studied. When using porphyrinic ligands, such SUR-MOFs are expected to have interesting applications in catalysis, electronic devices, and in photovoltaics. [26][27][28][29][30][31][32][33][34] Herein, we report a layer-by-layer epitaxial growth strategy for preparing SURMOFs with a layered structure. 2D sheets consisting of paddle-wheel (PW) units linked by porphyrin linkers are stacked by the interaction between layers being of van der Waals type. X-ray diffraction (XRD) data reveal that layer-by-layer deposition on appropriately functionalized substrates yields In this work, monolithic, crystalline, porous, and oriented porphyrin thin films are grown using a novel van der Waals layer-by-layer (lbl) epitaxial growth protocol, yielding an unusual AB-stacking motif of these interesting macrocycles units. Subsequently, these surface-mounted metal-organic frameworks (SURMOFs) are transformed by th...

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Section: Resultsmentioning

confidence: 99%

van der Waals Epitaxial Growth of 2D Metal–Porphyrin Framework Derived Thin Films for Dye‐Sensitized Solar Cells

Wang

Chen

Haldar

et al. 2018

Adv Materials Inter

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“…Transitions of such type is easily monitored by electrochemical methods allowing control of the reaction process . Mild oxidation of DTC in presence of various tetrapyrrolic mactoheterocycles was shown previously and catalytic properties of the macroheterocycle was found to be affected not only by metal cation but also by nature of terminal fragments providing spatial effects upon catalysis.…”

Section: Introductionmentioning

confidence: 52%

Sulfonated octa‐substituted Co(II) phthalocyanines immobilized on silica matrix as catalyst for Thiuram E synthesis

Вашурин

Marfin

Tarasyuk

et al. 2018

Applied Organom Chemis

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Silica nanoparticles were obtained during the work according to two different sol–gel methods. In first one Schtrober's technique and series of cobalt phthalocyanine metal complexes varying in peripheral substituents were used. Second method was performed using the same complexes but differed in applying surface‐active substance (SAS) and two precursors – tetraethoxysilane (TEOS) and aminopropyltrimethoxysilane (APTMOS). All obtained hybrid materials were analyzed via SEM, the size of single particle was studied, which in all cases was about 200 nm. In order to investigate hybrid's characteristics laser diffraction and liquid nitrogen adsorption methods were applied. Distinction in pore's specific volume of differently‐obtained nanoparticles was found. Catalytic activity of all obtained materials were tested in conversion of N,N‐diethylcarbamodithiolate to thiuram E. Effect of peripherally substituted phthalocyanines and morphology of matrixes were manifested on catalytic activity of the hybrids.

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“…Metal-coordination polymers are hybrid materials consisting of metal ions or clusters interconnected by rigid organic molecules (tectons) [ 1 , 2 ]. The ordering of the components in three dimensions, the possibility to use tectons of different natures and sizes, and the dynamic properties of the frameworks provide coordination polymers with unique luminescent, nonlinear optical, redox, magnetic, sorption, catalytic, ion exchange, sensory, and other properties [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ] Due to their structure and unique physicochemical and photophysical characteristics, particularlytheir photoactivity, optoelectronic, and electrochemical properties, tetrapyrrole molecules are extremely promising objects for the construction of metal-coordination polymers for various purposes [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. It is known that metal complexes of porphyrins and porphyrinoids are capable of selective reversible binding of substrate molecules and, thus, can be used to construct simple and complex supramolecular systems of various dimensions and architecture [ 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ].…”

Section: Introductionmentioning

confidence: 99%

New Polyporphyrin Arrays with Controlled Fluorescence Obtained by Diaxial Sn(IV)-Porphyrin Phenolates Chelation with Cu2+ Cation

et al. 2021

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New coordination oligomers and polymers of Sn(IV)-tetra(4-sulfonatophenyl)porphyrin have been constructed by the chelation reaction of its diaxialphenolates with Cu2+. The structure and properties of the synthesized polyporphyrin arrays were investigated by 1H Nuclear Magnetic Resonance (1H NMR), Infra Red (IR), Ultra Violet - Visible (UV-Vis) and fluorescence spectroscopy, mass spectrometry, Powder X-Rays Diffraction (PXRD), Electron Paramagnetic Resonance (EPR), thermal gravimetric, elemental analysis, and quantum chemical calculations. The results show that the diaxial coordination of bidentate organic ligands (L-tyrazine and diaminohydroquinone) leads to the quenching of the tetrapyrrole chromophore fluorescence, while the chelation of the porphyrinate diaxial complexes with Cu2+ is accompanied by an increase in the fluorescence in the organo-inorganic hybrid polymers formed. The obtained results are of particular interest to those involved in creating new ‘chemo-responsive’ (i.e., selectively interacting with other chemical species as receptors, sensors, or photocatalysts) materials, the optoelectronic properties of which can be controlled by varying the number and connection type of monomeric fragments in the polyporphyrin arrays.

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Layer-by-layer assembly of porphyrin-based metal–organic frameworks on solids decorated with graphene oxide

Abstract: Planar MOFs grow on graphene oxide templates.

Cited by 35 publications

References 42 publications

van der Waals Epitaxial Growth of 2D Metal–Porphyrin Framework Derived Thin Films for Dye‐Sensitized Solar Cells

van der Waals Epitaxial Growth of 2D Metal–Porphyrin Framework Derived Thin Films for Dye‐Sensitized Solar Cells

Sulfonated octa‐substituted Co(II) phthalocyanines immobilized on silica matrix as catalyst for Thiuram E synthesis

New Polyporphyrin Arrays with Controlled Fluorescence Obtained by Diaxial Sn(IV)-Porphyrin Phenolates Chelation with Cu2+ Cation

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