Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

Fonari, Alexandr; Corbin, Nathan; Vermeulen, Derek; Goetz, Katelyn P.; Jurchescu, Oana D.; McNeil, L. E.; Brédas, Jean‐Luc; Coropceanu, Veaceslav

doi:10.1063/1.4936965

Cited by 17 publications

(12 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The Kohn–Sham methods with periodic boundary conditions (periodic DFT) provide a grounded trade-off between the accuracy and the rate of calculations of experimentally observed properties of multi-component organic crystals [ 58 , 59 , 60 ]. The computations with all-electron Gaussian-type localized orbital basis 6-31G** were conducted using the CRYSTAL17 package [ 61 ].…”

Section: Methodsmentioning

confidence: 99%

Comparison of Proton Acceptor and Proton Donor Properties of H2O and H2O2 in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates

et al. 2022

View full text Add to dashboard Cite

Two new peroxosolvates of drug-like compounds were synthesized and studied by a combination of X-ray crystallographic, Raman spectroscopic methods, and periodic DFT computations. The enthalpies of H-bonds formed by hydrogen peroxide (H2O2) as a donor and an acceptor of protons were compared with the enthalpies of analogous H-bonds formed by water (H2O) in isomorphic (isostructural) hydrates. The enthalpies of H-bonds formed by H2O2 as a proton donor turned out to be higher than the values of the corresponding H-bonds formed by H2O. In the case of H2O2 as a proton acceptor in H-bonds, the ratio appeared reversed. The neutral O∙∙∙H-O/O∙∙∙H-N bonds formed by the lone electron pair of the oxygen atom of water were the strongest H-bonds in the considered crystals. In the paper, it was found out that the low-frequency Raman spectra of isomorphous crystalline hydrate and peroxosolvate of N-(5-Nitro-2-furfurylidene)-1-aminohydantoin are similar. As for the isostructural hydrate and peroxosolvate of the salt of protonated 2-amino-nicotinic acid and maleic acid monoanion, the Raman spectra are different.

show abstract

Section: Methodsmentioning

confidence: 99%

Comparison of Proton Acceptor and Proton Donor Properties of H2O and H2O2 in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates

et al. 2022

View full text Add to dashboard Cite

show abstract

“…Electronic Structure Calculations : Following the recent work, the geometry optimization of the β‐polymorph was performed by means of the αPBE functional with 30% nonlocal Hartree‐Fock exchange contribution and using the 6–31G basis set. The calculations were performed using a 6 × 8 × 6 Monkhorst‐Pack k ‐point mesh with a semi‐empirical dispersion correction.…”

Section: Methodsmentioning

confidence: 99%

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Goetz

Tsutsumi

Pookpanratana

et al. 2016

Adv Elect Materials

106

View full text Add to dashboard Cite

The organic charge-transfer (CT) complex dibenzotetrathiafulvalene – 7,7,8,8-tetracyanoquinodimethane (DBTTF-TCNQ) is found to crystallize in two polymorphs when grown by physical vapor transport: the known α-polymorph and a new structure, the β-polymorph. Structural and elemental analysis via selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), and polarized IR spectroscopy reveal that the complexes have the same stoichiometry with a 1:1 donor:acceptor ratio, but exhibit unique unit cells. The structural variations result in significant differences in the optoelectronic properties of the crystals, as observed in our experiments and electronic-structure calculations. Raman spectroscopy shows that the α-polymorph has a degree of charge transfer of about 0.5e, while the β-polymorph is nearly neutral. Organic field-effect transistors fabricated on these crystals reveal that in the same device structure both polymorphs show ambipolar charge transport, but the α-polymorph exhibits electron-dominant transport while the β-polymorph is hole-dominant. Together, these measurements imply that the transport features result from differing donor-acceptor overlap and consequential varying in frontier molecular orbital mixing, as suggested theoretically for charge-transfer complexes.

show abstract

“…The B3LYP(AtomOnly) approximation reproduces the position of the most intense low-lying vibration and provides a reasonable description of the spectrum in the considered frequency region ( Figure 5 To clarify the effect of cell parameter optimization on the Raman spectrum in the low-frequency region, calculations were performed in the PBE-D3(AtomOnly) approximation. Note that this approximation is used in periodic DFT computations with both GTO [77] and PW [78] We conclude that the approximations using cell parameter optimization cannot satisfactorily describe the low-frequency Raman spectrum of the crystals with intra-and intermolecular H bonds of different strengths. This is due to the overestimation of the thermal expansion of the crystals by PBE-D3 and B3LYP-D2 (Table 2 and Table S6, Supplementary Materials).…”

Section: Raman Spectrum In the Low-frequency Regionmentioning

confidence: 99%

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

et al. 2020

View full text Add to dashboard Cite

Synthesis of multicomponent solid forms is an important method of modifying and fine-tuning the most critical physicochemical properties of drug compounds. The design of new multicomponent pharmaceutical materials requires reliable information about the supramolecular arrangement of molecules and detailed description of the intermolecular interactions in the crystal structure. It implies the use of a combination of different experimental and theoretical investigation methods. Organic salts present new challenges for those who develop theoretical approaches describing the structure, spectral properties, and lattice energy Elatt. These crystals consist of closed-shell organic ions interacting through relatively strong hydrogen bonds, which leads to Elatt > 200 kJ/mol. Some technical problems that a user of periodic (solid-state) density functional theory (DFT) programs encounters when calculating the properties of these crystals still remain unsolved, for example, the influence of cell parameter optimization on the Elatt value, wave numbers, relative intensity of Raman-active vibrations in the low-frequency region, etc. In this work, various properties of a new two-component carbendazim maleate crystal were experimentally investigated, and the applicability of different DFT functionals and empirical Grimme corrections to the description of the obtained structural and spectroscopic properties was tested. Based on this, practical recommendations were developed for further theoretical studies of multicomponent organic pharmaceutical crystals.

show abstract

Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study

Cited by 17 publications

References 50 publications

Comparison of Proton Acceptor and Proton Donor Properties of H2O and H2O2 in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates

Comparison of Proton Acceptor and Proton Donor Properties of H2O and H2O2 in Organic Crystals of Drug-like Compounds: Peroxosolvates vs. Crystallohydrates

Polymorphism in the 1:1 Charge‐Transfer Complex DBTTF–TCNQ and Its Effects on Optical and Electronic Properties

Combined X-ray Crystallographic, IR/Raman Spectroscopic, and Periodic DFT Investigations of New Multicomponent Crystalline Forms of Anthelmintic Drugs: A Case Study of Carbendazim Maleate

Contact Info

Product

Resources

About