Noncovalent Interaction of Graphene with Heterocyclic Compounds: Benzene, Imidazole, Tetracene, and Imidazophenazines

Zarudnev, E. S.; Stepanian, S. G.; Adamowicz, Ludwik; Karachevtsev, V. A.

doi:10.1002/cphc.201500839

Cited by 25 publications

(21 citation statements)

References 45 publications

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“…Solomon and co‐workers [ 52 ] reported that noncovalent π–π stack between SLG and aromatic (benzene, anthracene) anchor can efficiently suppress phonon transport, leading to smaller phononic thermal conductance by an order of magnitude than that in the analogous junction with CC covalent contact at 300 K. The amine–SLG interaction (0.22 eV) is fivefold weaker than the π–π stack (1.01 eV), making our reasoning plausible. [ 27,53 ] Such a difference in the temperature drop between the covalent and noncovalent contacts is not trivial but cannot fully account for our observations. Our experiments (discussed below) indicate that the electronic structural effect contributes significantly to the observed difference in S values between SLG//H 2 NC n and Au/SC n SAMs.…”

Section: Resultsmentioning

confidence: 82%

Enhanced Thermopower of Saturated Molecules by Noncovalent Anchor‐Induced Electron Doping of Single‐Layer Graphene Electrode

Park

Kim

et al. 2021

Advanced Materials

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Enhancing thermopower is a key goal in organic and molecular thermoelectrics. Herein, it is shown that introducing noncovalent contact with a single-layer graphene (SLG) electrode improves the thermopower of saturated molecules as compared to the traditional gold-thiolate covalent contact. Thermoelectric junction measurements with a liquid-metal technique reveal that the value of Seebeck coefficient in large-area junctions based on n-alkylamine self-assembled monolayers (SAMs) on SLG is increased up to fivefold compared to the analogous junction based on n-alkanethiolate SAMs on gold. Experiments with Raman spectroscopy and field-effect transistor analysis indicate that such enhancements benefit from the creation of new in-gap states and electron doping through noncovalent interaction between the amine anchor and the SLG electrode, which leads to a reduced energy offset between the Fermi level and the transport channel. This work demonstrates that control of interfacial bonding nature in molecular junctions improves the Seebeck effect in saturated molecules.

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Section: Resultsmentioning

confidence: 82%

Enhanced Thermopower of Saturated Molecules by Noncovalent Anchor‐Induced Electron Doping of Single‐Layer Graphene Electrode

Park

Kim

et al. 2021

Advanced Materials

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“…36 However, the earlier literature on adsorption of N-heterocycles did not report anything about the involvement of N–H···π interactions. 10 In the case of complexes with doped Cor, d N–H···π is decreased with an increase in the number of N in the heterocyclic ring (especially for Tetra and Penta), suggesting the key role of N–H···π interaction in stabilizing their complexes, Table 1. For example, in the case of complexes involving Cor (3N) , d N–H···π decreases in the following order: Cor (3N) -Im (2.90) > Cor (3N) -Pz (2.78) > Cor (3N) -Pyr (2.77) > Cor (3N) -123-tria (2.75) > Cor (3N) -124-tria (2.73) > Cor (3N) -Tetra (2.65) > Cor (3N) -Penta (2.44); values are in angstrom.…”

Section: Results and Discussionmentioning

confidence: 99%

“…9,10,12 Zarudnev et al have reported the SE value of 7.90 kcal mol –1 for adsorption of Im on graphene (obtained at the M05-2X/6-31++G(d,p) level of theory) surface. 10 Although Im and Pz are isomeric/isoelectronic, SE values are relatively higher for Cor-Pz complexes (which may be attributed to the higher contribution from the N–H···π interaction, as evident from the N–H···π distance). This validates the importance of the position of N in the heterocycles in stabilizing the complexes.…”

Section: Results and Discussionmentioning

confidence: 99%

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Density Functional Study on the Adsorption of 5-Membered N-Heterocycles on B/N/BN-Doped Graphene: Coronene as a Model System

Saha¹,

Bhattacharyya

2018

ACS Omega

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Adsorption of seven 5-membered N-heterocycles on B/N/BN-doped graphene (with coronene as a model system) has been studied using density functional theory (DFT). The geometry of the complexes validated the involvement of both π···π stacking and N–H···π interaction in the adsorption process. The stability of the complexes is measured in terms of stabilization energy, and the results suggested that the complexes are stable enough (stabilization energies are in the range of 7.61–14.77 kcal mol –1 ). Studies confirmed the stability of complexes in the solvent phase too irrespective of the dielectric of the solvent. Dispersive force is the major mode of interaction in stabilizing the complexes. Natural bond orbital analysis indicated a small contribution from electrostatic and covalent interactions. Thermochemical analysis revealed that the complexation is exothermic in nature and favorable at a lower temperature. Adsorption of N-heterocycles exerts a nominal impact on the electronic properties of the undoped/doped graphene. The study presents a simple approach to introduce an arbitrary functionality to undoped/doped graphene by preserving its electronic properties.

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“…As aforementioned, nevertheless, either the substituent effect is attributed to π ‐ polarization or to local interaction, the substituent effects have been mostly rationalized with help of supermolecular approaches, and the role of substituents has been indirectly guessed from binding energy . Due to the size of the small stacked models, the hydrogens of the other ring may play role, as noticed by Rashkin and Waters .…”

Section: Introductionmentioning

confidence: 99%

On the role of substituent in noncovalent functionalization of graphene and organophosphor recognition: IQA and SAPT perspective

Javadi

Najafi

Yourdkhani

2017

Int J of Quantum Chemistry

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Despite importance of integrating organic molecules with graphene to fabricate graphene-based electronic devices, the role of substituents and interface stabilizing forces are poorly understood. In this work, the interactions of 7,7,8,2,3,5,7,8,, hydroquinone (Q), and tetrafluorohydroquinone (TFQ) with graphene have been investigated by means of interacting quantum atoms and SAPT(DFT). In addition, in context of potential design of a graphene-based sensor for detection of the nerve agent sarin, we studied the interaction of graphene and the organic molecules with the dimethyl methylphosphonate (DMMP)-the molecule that mimics sarin. The results show that the organic molecules attach to graphene via C(sp 2 )Á Á ÁC(sp 2 ), C(sp 2 )Á Á ÁC (sp) and HÁ Á Áp bonds. In addition, they trap DMMP via various linkages such as hydrogen, lonepairÁ Á Áp and HÁ Á Áp. The quantum effects play a significant role. The Pauli repulsion is responsible for p-doping of graphene. The substituents are stabilized on graphene by the exchange-correlation energy. The fluorination of the benzenoid ring raises the electron-sharing. The through space and through bond effects of the fluorine atoms (-F) increase the classical attraction of the cyano groups and benzenoid ring with graphene, respectively. When comparing performance of the ab initio and DFT methods, MP2 predicts too much attraction due to well-known overestimation of the dispersion energy by the uncoupled dispersion component for benzene rings, while xB97xD functional and SAPT(DFT) provide weaker interaction energies, in good agreement with each other. K E Y W O R D S graphene, interacting quantum atoms, noncovalent functionalization, SAPT, substituent effects | I N T R O D U C T I O NDue to the extraordinary properties, [1][2][3][4] graphene [5] is regarded as a promising material in various devices such as capacitors, [6][7][8] nanoelectronic devices, [9] and sensors. [10,11] Despite the superior properties of graphene, its zero band gap and its low reactivity as compared to other nanostructured carbon allotropes, [12,13] are two major obstacles for using graphene as a semiconductors or sensor. Therefore, forcing a sizable band gap and overcoming the inertness are crucial for utilization of graphene in nanoscale devices. [14][15][16] Noncovalent functionalization of graphene [16] through adsorption of organic molecules on its surface, [17] that is, surface charge transfer doping, [18][19][20][21] is a safe strategy for tuning electrical properties of graphene without damaging sp 2 carbon network of graphene. [16] Based on the nature of organic molecule adsorbed onto the graphene surface, electrons are moved to or pushed away from graphene through charge transfer (CT) interaction, [22,23] leading to tuning the electronic structure of graphene. It is parenthetically worth mentioning that it is better to consider CT interaction as a part of induction energy. [24] Regardless of the nature of adsorbates-either donor or acceptor-however, they are stabilized on the graphene surface via no...

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Noncovalent Interaction of Graphene with Heterocyclic Compounds: Benzene, Imidazole, Tetracene, and Imidazophenazines

Cited by 25 publications

References 45 publications

Enhanced Thermopower of Saturated Molecules by Noncovalent Anchor‐Induced Electron Doping of Single‐Layer Graphene Electrode

Enhanced Thermopower of Saturated Molecules by Noncovalent Anchor‐Induced Electron Doping of Single‐Layer Graphene Electrode

Density Functional Study on the Adsorption of 5-Membered N-Heterocycles on B/N/BN-Doped Graphene: Coronene as a Model System

On the role of substituent in noncovalent functionalization of graphene and organophosphor recognition: IQA and SAPT perspective

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