Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2‐bis(4‐pyridyl)ethylene and Phloroglucinol:Phenazine

Dubey, Ritesh; Desiraju, Gautam R.

doi:10.1002/ange.201402668

Cited by 5 publications

(4 citation statements)

References 43 publications

(20 reference statements)

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“…Accordingly, we selected a polyhydric phenol (ORC, PGL), a heterocyclic base (TMP, DPE-I, DPE-II), and PAHs as precursors. 51 In the second step, O−H•••N is the preferred hydrogen bond, along with other weaker variants of interactions available in solution. In the third step, a skilful selection of a template molecule is applied to quench certain interaction possibilities, effectively leading to the fittest set.…”

Section: ■ Combinatorial Crystal Synthesismentioning

confidence: 99%

“…In 2014, we reported six distinct cocrystal polymorphs of PGL:DPE-I. 51 When DPE-I was replaced by PHE, the resulting PGL:PHE cocrystal was obtained in seven distinct crystal forms. Cocrystal polymorphism is not very common, and so the appearance of multiple crystal structures in these systems hints at the presence of competitive and kinetically favored synthons in solution.…”

Section: ■ Combinatorial Crystal Synthesismentioning

confidence: 99%

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Strategy and Methodology in the Synthesis of Multicomponent Molecular Solids: The Quest for Higher Cocrystals

2019

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CONSPECTUS: Crystal engineering is the art and science of making crystals by design. Crystallization is inherently a purifying phenomenon. Bringing together more than one organic compound into the same crystal always needs deliberate action. Cocrystals are important because they offer a route to the controlled modulation of crystal properties. The route to cocrystal synthesis was opened up with the heterosynthon concept, which considers the complementary recognition of chemical groups from different molecules. Using this concept, binary cocrystals of enormous variety have been generated, even as crystal engineering has evolved into a form of solid-state supramolecular synthesis. Introducing a third component (a component is somewhat arbitrarily defined as an organic substance that is a solid at room temperature, mostly with the idea of excluding solvates) in a stoichiometric manner requires substantially greater effort and a careful balance of intermolecular interactionstheir strengths, directional properties, and distance falloff characteristics. The first systematic ternary cocrystal synthesis was reported around 15 years ago. Drawing in a fourth component in stoichiometric amounts is exceedingly difficult, and we reported such syntheses in 2016. To date, a limited number of ternary cocrystals have been realized (around 120 in all, with a half from our group) and an even smaller number of quaternary cocrystals (around 30, all from our group, barring one). It is impressive that our experiments largely yielded the intended higher cocrystal (three-or four-component) with very small traces of contaminating binaries and pure compounds. A fifth or sixth component may be brought into the solid in the manner of a solid solution in that these components are situated at one of the sites of the quaternary cocrystal. To date, five components have not been included stoichiometrically within the same crystal. This is still an open challenge. The merit in synthesizing (higher) cocrystals is that one can systematically engineer property modularity: Each component is associated with a distinct property. This is important in the pharmaceutical industry, where each component can, in principle, confer a different, desirable propertydrug action, solubility, or permeability. However, difficult synthetic targets are also addressed in chemistry simply because they are there. The intellectual satisfaction in making something that is very difficult to make renders the enterprise worthwhile in itself, and new chemistry usually gets uncovered in the process. The development of synthetic organic chemistry can undoubtedly be credited to various reliable methods for chemical transformations, and many difficult total syntheses were achieved by employing these methods over two centuries of research. In contrast, supramolecular synthesis (of multicomponent cocrystals and other assemblies) is in no way at a similar level of sophistication because the subject is still relatively young. Our group and others have reported the synthesis of many hi...

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Section: ■ Combinatorial Crystal Synthesismentioning

confidence: 99%

Section: ■ Combinatorial Crystal Synthesismentioning

confidence: 99%

Strategy and Methodology in the Synthesis of Multicomponent Molecular Solids: The Quest for Higher Cocrystals

2019

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“…Drop-casting of a very dilute solution (20 μM) of SA R on carbon-coated copper grid clearly resolves lattice spacing of 0.21 nm (Figure S8). 56 Such lattice spacings are also present in H-bonded molecular clusters. Thus, we can assert here that the functional groups (hydroxyl and amine) of monomer contribute to form self-assembly in solid-state.…”

Section: Resultsmentioning

confidence: 93%

Continuous Making, Stretch Breaking, and Exciton Dynamics of a Red-Emissive Organic Submicrometer-Sized Triangular Pyramid

et al. 2023

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Highly photoluminescent, single-component self-assembly being scalable and sustainable has a profound commercial significance. In this article, the challenges that we address in development of self-assembly of π-conjugated molecules are (i) feeble photoluminescence caused by poor molecular orientational ordering and (ii) costly fluorescent monomer owing to lack of an atom/step/energy economical synthetic method. We have discovered that a bright yellow fluorescent xanthene analog capable of instantly forming self-assembly can be synthesized by a home-built coil-in-spiral reactor using an inexpensive precursor, pyrogallol. Stimuli such as temperature (35 °C), acid fumes, and apolar solvent can trigger the formation of red-emissive self-assembly. In solution orientation of about 13 molecules yielding hydrogen-bonded self-assembly has a direct resemblance with a Coulomb-coupled J-aggregate highlighted in the Kasha model. After photoexcitation, the excited state dynamics of the monomer progress via three pathways: (i) relaxation (2 ± 0.3 ps), (ii) solvation (19.5 ± 3 ps), and (iii) decay (2.5 ns). On the other hand, self-assembly exciton evolves via two pathways: (i) relaxation (81 ± 25 ps) and (ii) decay (∼1 ns). In the solid state, the self-assembly retains the submicron-sized trigonal pyramidal structures by layer-by-layer stacking of triangular plates. This self-assembly doped in polymer even exhibits mechanofluorescence. Our study will pave way the use of this photoluminescent self-assembly for improved performance of organic/sustainable electronics and stretchable electronics.

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“…The targeting synthon-based crystallization was enhanced by chosen conformers combination to obtain stoichiometric ternary solids. At this point, it is necessary to clarify that ternary cocrystals are molecular solids containing three discrete solid organic compounds in their basic unit cell [ 28 ]. The applied procedure is equivalent to the combinatorial synthesis of crystals.…”

Section: Introductionmentioning

confidence: 99%

Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection

Panek

Zasada

Szyja

et al. 2021

IJMS

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The O-H...N and O-H...O hydrogen bonds were investigated in 10-hydroxybenzo[h]quinoline (HBQ) and benzo[h]quinoline-2-methylresorcinol complex in vacuo, solvent and crystalline phases. The chosen systems contain analogous donor and acceptor moieties but differently coupled (intra- versus intermolecularly). Car–Parrinello molecular dynamics (CPMD) was employed to shed light onto principle components of interactions responsible for the self-assembly. It was applied to study the dynamics of the hydrogen bonds and vibrational features as well as to provide initial geometries for incorporation of quantum effects and electronic structure studies. The vibrational features were revealed using Fourier transformation of the autocorrelation function of atomic velocity and by inclusion of nuclear quantum effects on the O-H stretching solving vibrational Schrödinger equation a posteriori. The potential of mean force (Pmf) was computed for the whole trajectory to derive the probability density distribution and for the O-H stretching mode from the proton vibrational eigenfunctions and eigenvalues incorporating statistical sampling and nuclear quantum effects. The electronic structure changes of the benzo[h]quinoline-2-methylresorcinol dimer and trimers were studied based on Constrained Density Functional Theory (CDFT) whereas the Electron Localization Function (ELF) method was applied for all systems. It was found that the bridged proton is localized on the donor side in both investigated systems in vacuo. The crystalline phase simulations indicated bridged proton-sharing and transfer events in HBQ. These effects are even more pronounced when nuclear quantization is taken into account, and the quantized Pmf allows the proton to sample the acceptor area more efficiently. The CDFT indicated the charge depletion at the bridged proton for the analyzed dimer and trimers in solvent. The ELF analysis showed the presence of the isolated proton (a signature of the strongest hydrogen bonds) only in some parts of the HBQ crystal simulation. The collected data underline the importance of the intramolecular coupling between the donor and acceptor moieties.

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Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2‐bis(4‐pyridyl)ethylene and Phloroglucinol:Phenazine

Cited by 5 publications

References 43 publications

Strategy and Methodology in the Synthesis of Multicomponent Molecular Solids: The Quest for Higher Cocrystals

Strategy and Methodology in the Synthesis of Multicomponent Molecular Solids: The Quest for Higher Cocrystals

Continuous Making, Stretch Breaking, and Exciton Dynamics of a Red-Emissive Organic Submicrometer-Sized Triangular Pyramid

Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection

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