Non‐Covalent Chemistry of Graphene: Electronic Communication with Dendronized Perylene Bisimides

Kozhemyakina, Nina V.; Englert, Jan M.; Yang, Guang; Spiecker, Erdmann; Schmidt, Cordula D.; Hauke, Frank; Hirsch, Andreas

doi:10.1002/adma.201003206

Cited by 128 publications

(133 citation statements)

References 16 publications

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“…TheH OMO-LUMO excitation of PDI-functionalized antimonene sheets is thus of charge transfer character.T he antimonene/BP band structures themselves show only minor changes upon adsorption of PDI (see the Supporting Information for details). [30] However, because of the "PDI band" forming the lowest unoccupied band, the calculated band gap of the PDI-antimonene system is 1.05 eV,that is,the adsorption-induced band gap change is À0.75 eV,and in good accordance with the XPS experiments.…”

Section: Angewandte Chemiesupporting

confidence: 67%

“…This family of compounds exhibits high performance in the functionalization of several nanomaterials such as carbon nanotubes,g raphene,m olybdenum disulfide (MoS 2 ), and BP. [27,[29][30][31] TheR aman characterization of very thin antimonene flakes,o btained by microexfoliation, is challenging because of the very low non-resonant Raman intensities,asrecently reported by our group. [12,13] Therefore, fast detection of the exfoliated flakes is precluded by Raman spectroscopy,s ow eh ave recently optimized optical microscopy conditions to facilitate the identification of few-layer antimonene flakes.…”

Section: Two-dimensional (2d) Materials Have Attracted Enormousmentioning

confidence: 91%

“…Thes ign of the shift indicates that these Sb species are oxidized with respect to metallic Sb,but the charge transfer is less pronounced than in the oxide.These results indicate that the functionalizing molecule acts as an electron acceptor,w hich fits perfectly with the electronwithdrawing behavior exhibited by PDI molecules on other related 2D materials. [27,30] To complement the experimental results,the supramolecular interaction of our PDI on antimonene was systematically investigated by DFT calculations.C oncretely,P DI, taking into account the p core and the first methyl group of the peripheral branches for reducing the computational effort, was modeled (Figure 3; see the Supporting Information). We also computed one peripheral branch with half of the PDI core adsorbed on antimonene,and thus further confirmed the parallel disposition of the PDI core with respect to the antimonene surface (see Figure S14).…”

Section: Angewandte Chemiementioning

confidence: 99%

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Noncovalent Functionalization and Charge Transfer in Antimonene

et al. 2017

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Antimonene,anovel group 15 two-dimensional material, is functionalizedwith atailormade perylene bisimide through strong van der Waals interactions.T he functionalization process leads to as ignificant quenching of the perylene fluorescence,a nd surpasses that observed for either graphene or black phosphorus,thus allowing straightforwardc haracterization of the flakes by scanning Raman microscopy. Furthermore,s canning photoelectron microscopys tudies and theoretical calculations reveal ar emarkable charge-transfer behavior,being twice that of black phosphorus.Moreover,the excellent stability under environmental conditions of pristine antimonene has been tackled,t hus pointing towards the spontaneous formation of asub-nanometric oxide passivation layer.D FT calculations revealed that the noncovalent functionalization of antimonene results in ac harge-transfer band gap of 1.1 eV.Two-dimensional (2D) materials have attracted enormous attention during the last few years because of their outstanding properties and applications. [1][2][3] Beyond gapless graphene,o ther elemental 2D materials have been successfully synthesized, with black phosphorus (BP) being the only semiconducting material reported so far. [4][5][6][7] This result together with its excellent charge-carrier mobility and current on/off ratios renders BP ap erfect candidate for nanoelectronics and nanophotonics.H owever,i ts (in)stability represents am ajor drawback for the development of the real applications. [8][9][10][11] In contrast, its relative in the periodic table, antimonene,that is,asingle layer of antimony,exhibits aband gap of about 1.8-2.4 eV and an outstanding stability under ambient conditions.A ntimonene has been recently isolated for the very first time both by mechanical exfoliation [12] and liquid-phase exfoliation [13] as reported by our groups.A number of theoretical calculations predict extraordinary physical properties like high carrier mobility, [14] thermal conductivity, [15] and strain-induced band transition, [16] among others.Therefore,a ntimonene appears to be ap romising platform for high-performance sensors, [17] double-gate MOSFETs, [18] spintronics, [19,20] optoelectronic applications, [21,22] energy storage and conversion, [23] and biomedicine.[24]Recently,v an der Waals and molecular beam epitaxy (MBE) have been applied for the synthesis of antimonene on different surfaces,t hereby exhibiting good stabilities and high electrical conductivities of up to 10 4 Sm À1 in about 30 nm thick flakes. [25,26] Despite synthetic efforts,t he chemistry and therefore the molecular doping of antimonene remains completely unexplored. In relation to that, we have recently reported on the noncovalent functionalization of BP with electron-poor and polarizable polycyclic aromatic molecules, thus observing ar emarkable charge-transfer behavior, and improving the resistance of the flakes against oxygen degradation.[ 27,28] In this context, the present work nicely illustrates,for the first time,the noncovalent functionalization o...

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Section: Angewandte Chemiesupporting

confidence: 67%

Section: Two-dimensional (2d) Materials Have Attracted Enormousmentioning

confidence: 91%

Section: Angewandte Chemiementioning

confidence: 99%

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Noncovalent Functionalization and Charge Transfer in Antimonene

et al. 2017

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“…Perylenes: Several perylene-based DSAs have been used to promote the exfoliation of graphite in aqueous solutions, including sophisticated perylene diimide (PDI)-based bolaamphiphiles [200,221] (PDIBBA; Figure 8) and PDI-sulfonic acid (PDI (SO 3 ) 2 ). [202] An effective and efficient method for the preparation of graphene by UILPE in aqueous dispersions, was demonstrated by Stupp, Stoddart and co-workers, [222] by using N,N′-dimthyl-2,9-diazaperopyrenuim dichloride (PDAP; see Figure 8) molecules to stabilize dispersed graphene sheets in water via electrostatic repulsion between the positively charged PDAPs physisorbed on graphene flakes.…”

Section: Reviewmentioning

confidence: 99%

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

2016

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Graphene, a one-atom thick two-dimensional (2D) material, is at the core of an ever-growing research effort due to its combination of unique mechanical, thermal, optical and electrical properties. Two strategies are being pursued for the graphene production: the bottom-up and the top-down. The former relies on the use of covalent chemistry approaches on properly designed molecular building blocks undergoing chemical reaction to form 2D covalent networks. The latter occurs via exfoliation of bulk graphite into individual graphene sheets. Amongst the various types of exfoliations exploited so far, ultrasound-induced liquid-phase exfoliation (UILPE) is an attractive strategy, being extremely versatile, up-scalable and applicable to a variety of environments. In this review, we highlight the recent developments that have led to successful non-covalent functionalization of graphene and how the latter can be exploited to promote the process of molecule-assisted UILPE of graphite. The functionalization of graphene with non-covalently interacting molecules, both in dispersions as well as in dry films, represents a promising and modular approach to tune various physical and chemical properties of graphene, eventually conferring to such a 2D system a multifunctional nature.

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“…Kozehemyakina and co-workers, [ 84 ] attributed the quenching of perylene bismide fl uorescence by the presence of graphene in the solid state to a photo-induced electron transfer mechanism. The empty states in the conduction band above the Fermi level in graphene could act as acceptor for the photoexcited electron of the dye, whereas the fi lled valence band of graphene could act as a donor for electrons able to refi ll the remaining holes in the ground state of the dye.…”

Section: Optical Propertiesmentioning

confidence: 99%

Interphases in Graphene Polymer‐based Nanocomposites: Achievements and Challenges

et al. 2011

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Graphene constitutes a two dimensional sp2 hybridized carbon material with outstanding electrical and mechanical properties. To date, novel methods for producing large quantities of graphene and its derivatives (doped or functionalized graphenes, nanoribbons and nanoplatelets) are emerging, and research dedicated to the fabrication of polymer nanocomposites using graphenes has started. In this Research News, we summarize the synthesis and properties of graphene and its derivatives, and provide an overview of the latest research dedicated to the fabrication of polymer composites for different applications, including mechanical, electrical, optical and thermal. Some of the recently fabricated composites exhibit outstanding properties, however, it is vital to understand the chemistry and physics of the interphases established between the polymer and the graphene surfaces. The challenges in the fabrication of super robust and highly conducting composites using graphenes are also discussed. It is believed that graphene‐based polymer composites will result in commercial products if their interphases and reactivity are carefully controlled.

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Non‐Covalent Chemistry of Graphene: Electronic Communication with Dendronized Perylene Bisimides

Cited by 128 publications

References 16 publications

Noncovalent Functionalization and Charge Transfer in Antimonene

Noncovalent Functionalization and Charge Transfer in Antimonene

Supramolecular Approaches to Graphene: From Self‐Assembly to Molecule‐Assisted Liquid‐Phase Exfoliation

Interphases in Graphene Polymer‐based Nanocomposites: Achievements and Challenges

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