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69 Publications visible to you, out of a total of 69
Read between the Molecules: Computational Insights into Organic Semiconductors

Abstract (Expand)

The performance and key electronic properties of molecular organic semiconductors are dictated by the interplay between the chemistry of the molecular core and the intermolecular factors of which … manipulation has inspired both experimentalists and theorists. This Perspective presents major computational challenges and modern methodological strategies to advance the field. The discussion ranges from insights and design principles at the quantum chemical level, in-depth atomistic modeling based on multiscale protocols, morphological prediction and characterization as well as energy-property maps involving data-driven analysis. A personal overview of the past achievements and future direction is also provided.

Authors: Ganna Gryn’ova, Kun-Han Lin, Clémence Corminboeuf

Date Published: 5th Nov 2018

Publication Type: Journal

Noncovalent Molecular Electronics

Abstract (Expand)

Molecular electronics covers several distinctly different conducting architectures, including organic semiconductors and single-molecule junctions. The noncovalent interactions, abundant in the former, … are also often found in the latter, i.e., the dimer junctions. In the present work, we draw the parallel between the two types of noncovalent molecular electronics for a range of π-conjugated heteroaromatic molecules. In silico modeling allows us to distill the factors that arise from the chemical nature of their building blocks and from their mutual arrangement. We find that the same compounds are consistently the worst and the best performers in the two types of electronic assemblies, emphasizing the universal imprint of the underlying chemistry of the molecular cores on their diverse charge transport characteristics. The interplay between molecular and intermolecular factors creates a spectrum of noncovalent conductive architectures, which can be manipulated using the design strategies based upon the established relationships between chemistry and transport.

Authors: G. Gryn’ova, C. Corminboeuf

Date Published: 17th Apr 2018

Publication Type: Journal

Steric “Attraction”: Not by Dispersion Alone

Abstract (Expand)

Non-covalent interactions between neutral, sterically hindered organic molecules generally involve a strong stabilizing contribution from dispersion forces that in many systems turns the ‘steric … repulsion’ into a ‘steric attraction’. In addition to London dispersion, such systems benefit from electrostatic stabilization, which arises from a short-range effect of charge penetration and gets bigger with increasing steric bulk. In the present work, we quantify this contribution for a diverse set of molecular cores, ranging from unsubstituted benzene and cyclohexane to their derivatives carrying tert-butyl, phenyl, cyclohexyl and adamantyl substituents. While the importance of electrostatic interactions in the dimers of sp2-rich (e.g., π-conjugated) cores is well appreciated, less polarizable assemblies of sp3-rich systems with multiple short-range CH···HC contacts between the bulky cyclohexyl and adamantyl moieties are also significantly influenced by electrostatics. Charge penetration is drastically larger in absolute terms for the sp2-rich cores, but still has a non-negligible effect on the sp3-rich dimers, investigated herein, both in terms of their energetics and equilibrium interaction distances. These results emphasize the importance of this electrostatic effect, which has so far been less recognized in aliphatic systems compared to London dispersion, and are therefore likely to have implications for the development of force fields and methods for crystal structure prediction.

Authors: Ganna Gryn’ova, Clémence Corminboeuf

Date Published: 2018

Publication Type: Journal

Fine-Tuned Organic Photoredox Catalysts for Fragmentation-Alkynylation Cascades of Cyclic Oxime Ethers

Abstract (Expand)

Fine-tuned organic photoredox catalysts are introduced for the metal-free alkynylation of alkylnitrile radicals generated via oxidative ring opening of cyclic alkylketone oxime ethers. The redox … properties of the dyes were determined by both cyclic voltammetry and computation and covered an existing gap in the oxidation potential of photoredox organocatalysts.

Authors: Franck Le Vaillant, Marion Garreau, Stefano Nicolai, Ganna Gryn'ova, Clemence Corminboeuf, Jerome Waser

Date Published: 2018

Publication Type: Journal

Heterotetracenes: Flexible Synthesis and in Silico Assessment of the Hole-Transport Properties

Abstract (Expand)

Thienoacenes and furoacenes are among the most frequent molecular units found in organic materials. The efficient synthesis of morphologically different heteroacenes and the rapid determination of their … solid‐state and electronic properties are still challenging tasks, which slow down progress in the development of new materials. Here, we report a flexible and efficient synthesis of unprecedented heterotetracenes based on a platinum‐ and gold‐catalyzed cyclization–alkynylation domino process using EthynylBenziodoXole (EBX) hypervalent iodine reagents in the key step. The proof‐of‐principle in silico estimation of the synthesized tetracenes’ charge transport properties reveals their strong dependence on both the position and nature of the heteroatoms in the ring system. A broad range of mobility is predicted, with some compounds displaying performance potentially comparable to that of state‐of‐the‐art electronic organic materials.

Authors: Yifan Li, Ganna Gryn'ova, Felipe Saenz, Xavier Jeanbourquin, Kevin Sivula, Clémence Corminboeuf, Jérôme Waser

Date Published: 12th Jun 2017

Publication Type: Journal

Computational Design of pH-Switchable Control Agents for Nitroxide Mediated Polymerization

Abstract (Expand)

In the present work we use accurate quantum chemistry to evaluate several known and novel nitroxides bearing acid–base groups as pH-switchable control agents for room temperature NMP. Based on … G3(MP2,CC)(+)//M06-2X/6-31+G(d) calculations with UAKS-CPCM/M06-2X/6-31+G(d) solvation corrections, a number of novel nitroxides are predicted to be suitable for controlled polymerization of bulk styrene at room temperature when deprotonated (i.e. negatively charged), while remaining inert when neutral. These include an α-ethyl analogue of 3-carboxy-PROXYL and novel derivatives of 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) that have been modified to include acidic groups. Among the other species evaluated, 3,4-dicarboxy-PROXYL, α-carboxylated PROXYL and the phosphoric acid derivative of N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1) are predicted to undergo suitable pH-switching at around 60 °C, and may also be fitting for some applications.

Authors: Ganna Gryn’ova, Leesa M. Smith, Michelle L. Coote

Date Published: 2017

Publication Type: Journal

Guidelines and Diagnostics for Charge Carrier Tuning in Thiophene-Based Wires

Abstract (Expand)

Reported experimental trends in charge carrier tuning in single molecule junctions of oligothiophene-based wires are rationalized by means of frontier molecular orbital theory. The length and substituent … effects on the energy levels of the frontier orbitals have been shown to translate to the computed transmission spectra – with a caveat of the role of the linker group. The resulting transport (charge carrier) type – n- (electrons) or p- (holes) – is easily identifiable from the in silico charge transfer trends.

Authors: Ganna Gryn'ova, Pauline J. Ollitrault, Clémence Corminboeuf

Date Published: 2017

Publication Type: Journal

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