Interactions between an Aryl Thioacetate‐Functionalized Zn(II) Porphyrin and Graphene Oxide

Mao, Boyang; Calatayud, David G.; Mirabello, Vincenzo; Hodges, Benjamin J.; Martins, José A.; Botchway, Stanley W.; Mitchels, John M.; Pascu, Sofia I.

doi:10.1002/adfm.201504147

Cited by 17 publications

(18 citation statements)

References 48 publications

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“…The porphyrin systems of choice were: meso‐tetraphenylporphyrin, 1 , 5,10,15,20‐tetrakis(pentafluorophenyl)porphyrin, 2 , a perfluorinated derivative of 1 , as well as 5,15‐di(3‐acetylthiomethylphenyl)‐2,8,12,18‐tetra‐n‐hexyl‐3,7,13,17‐tetramethylporphyrin, a bulky derivative denoted 3 . The bulky porphyrin 3 has been previously synthesised on a laboratory scale and employed hereby for the in situ transformation because, unlike porphyrins 1 and 2 , this compound exhibits two aryl thioacetate‐functionalised side groups at the meso ‐positions and four hexyl chains at the β ‐position which increase the overall hydrophobicity and solubility in most common organic solvents . For porphyrin 3 , the single crystal X‐ray diffraction studies showed that molecules are oriented face‐on and show two hexyl chain groups placed anti with respect to the aromatic core .…”

Section: Resultsmentioning

confidence: 99%

“…The bulky porphyrin 3 has been previously synthesised on a laboratory scale and employed hereby for the in situ transformation because, unlike porphyrins 1 and 2 , this compound exhibits two aryl thioacetate‐functionalised side groups at the meso ‐positions and four hexyl chains at the β ‐position which increase the overall hydrophobicity and solubility in most common organic solvents . For porphyrin 3 , the single crystal X‐ray diffraction studies showed that molecules are oriented face‐on and show two hexyl chain groups placed anti with respect to the aromatic core . This free base porphyrin incorporating functionalised hexyl chains was selected as these aliphatic groups were deemed able to separate individual porphyrins from other molecular species.…”

Section: Resultsmentioning

confidence: 99%

“…Tailored‐made functional porphyrins can direct the formation of complex structures when self‐assembled onto the graphene oxide surfaces and exhibit optoelectronic properties that retain the characteristic of the original porphyrin in terms of emission properties. These systems can also sense the local environment and can become a probe for local inhomogeneity in electronic properties, as evidenced by subtle changes in the fluorescence lifetime elucidated by imaging investigations in thin film . The directed‐ and self‐assembly mechanisms appeared to impart accurate thermodynamic control over the nature of supramolecular polymerisation of Zn(II)‐derivatised porphyrins onto graphene oxides or carbon nanotubes graphitic surfaces and the morphologies of the hybrids formed appear to be governed by a subtle balance between molecule‐graphene, molecule‐molecule, solvent‐graphene and molecule‐solvent interactions …”

Section: Introductionmentioning

confidence: 99%

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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: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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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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“…Tyson emerged. [9][10][11] The functionalization of carbon-based nanomaterials, especially CNTs and graphene, is extremely attractive in the bioanalytical area for electrode design as they can combine properties of the high surface area, acceptable biocompatibility, chemical and electrochemical stability, and good electrical conductivity., [ 12,13 ] For instance, CNTs demonstrate faster response time and higher sensitivity than traditional electrodes. Such improved performance is attributed to their 1D hollow tubular nanochemistry that is responsible for the effi cient capture and promotion of electron transfer from analytes.…”

Section: Thermally Reduced Graphene Oxide Nanohybrids Of Chiral Functmentioning

confidence: 99%

Thermally Reduced Graphene Oxide Nanohybrids of Chiral Functional Naphthalenediimides for Prostate Cancer Cells Bioimaging

Tyson

Mirabello

Calatayud

et al. 2016

Adv Funct Materials

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This study reports on the supramolecular assemblies formed between planar carbon systems (PCSs) such as thermally reduced graphene oxide (TRGO) and its small‐molecule model system coronene and a series of d‐ and l‐α amino acid derivatized naphthalenediimides (NDIs) where the halogen substituents (X = F, Cl, Br, I) are varied systematically. Confocal fluorescence microscopy of NDIs, NDI•coronene, and NDI•TRGO complexes is performed proving the uptake and stability of such complexes in the cellular environment and suggesting their potential as prostate cancer imaging agents. 1H NMR and UV–vis spectroscopy studies support the formation of charge transfer complexes whereby the increasing polarizability and general electronegativity of the aryl halide substituted at the NDI periphery influence the magnitude of the association constants in the ground state between NDI and coronene. Complexation between NDIs and PCSs also results in stable photoexcited assemblies within the solution (coronene) as well as the dispersed phased (TRGO). Fluorescence emission titrations and 2‐photon time correlated single photon counting measurements suggest the existence of dynamic quenching mechanisms upon the excitation of the fluorophore in the presence of the carbon substrates, as these methods are sensitive proves for the subtle changes in the NDI environment. The series of halogenated species used exerts supramolecular control over the degree of surface assembly on the TRGO and over the interactions with the coronene molecule, and this is of relevance to the assembly of future biosensing platforms as these materials can both be viewed as congeners of graphene. Finally, MTT assays carried out in PC‐3 cells demonstrate that the stable noncovalent functionalization of TRGO and coronene with either l or d NDIs remarkably improves the cellular viability in the presence of such graphene‐like materials. These phenomena are of particular relevance for the understanding of the direct donor–acceptor interactions in solutions which govern the design of nanomaterials with future biosensing and bioimaging applications.

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“…S1, ESI †). [34][35][36] GO can be coated directly onto a cellulose surface via H-bonding (Scheme 1). Thus, immersing a cellulose film with a GO suspension is an efficient approach to modify the cellulose membrane, which not only enhances the binding ability between the cellulose film and fluorescent molecules through a stacking process, but also influences the surface wettability.…”

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confidence: 99%

Fluorescence detection and removal of copper from water using a biobased and biodegradable 2D soft material

Liu

Wang

et al. 2018

Chem. Commun.

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We have developed a green and robust fluorogenic (λ = 410 nm, λ = 510 nm) cellulose membrane using graphene oxide (GO) as a construct for simultaneous copper ion recognition and filtration at environmentally relevant levels. The detection limit and removal limit of Cu are 7.3 × 10 M and 1000 ppm, respectively. The simplicity and scalability achieved for the detection and removal of metal ions in waste water is particularly noteworthy given the significant problems associated with metal ion pollution of drinking water.

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Interactions between an Aryl Thioacetate‐Functionalized Zn(II) Porphyrin and Graphene Oxide

Cited by 17 publications

References 48 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

Thermally Reduced Graphene Oxide Nanohybrids of Chiral Functional Naphthalenediimides for Prostate Cancer Cells Bioimaging

Fluorescence detection and removal of copper from water using a biobased and biodegradable 2D soft material

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