scholarly journals Solvophobicity-directed assembly of microporous molecular crystals

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Hiroshi Yamagishi ◽  
Monika Tsunoda ◽  
Kohei Iwai ◽  
Kowit Hengphasatporn ◽  
Yasuteru Shigeta ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Driving Force ◽  
Computational Analysis ◽  
Organic Molecules ◽  
Molecular Crystals ◽  
Directed Assembly ◽  
Dispersion Interaction ◽  
Solvophobic Effect ◽  
Intermolecular Bonding

AbstractDense packing is a universal tendency of organic molecules in the solid state. Typical porous crystals utilize reticular strong intermolecular bonding networks to overcome this principle. Here, we report a solvophobicity-based methodology for assembling discrete molecules into a porous form and succeed in synthesizing isostructural porous polymorphs of an amphiphilic aromatic molecule Py6Mes. A computational analysis of the crystal structure reveals the major contribution of dispersion interaction as the driving force for assembling Py6Mes into a columnar stacking while the columns are sterically salient and form nanopores between them. The porous packing is facilitated particularly in solvents with weak dispersion interaction due to the solvophobic effect. Conversely, solvents with strong dispersion interaction intercalate between Py6Mes due to the solvophilic effect and provide non-porous inclusion crystals. The solvophobicity-directed polymorphism is further corroborated by the polymorphs of Py6Mes-analogues, m-Py6Mes and Ph6Mes.

scholarly journals Room-Temperature Mg-Ion Conduction Through Molecular Crystal Mg{N(SO2CF3)2}2(CH3OC5H9)2

2021 ◽  
Vol 9 ◽  
Author(s):  
Takaaki Ota ◽  
Shota Uchiyama ◽  
Keiichi Tsukada ◽  
Makoto Moriya
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Ionic Conductivity ◽  
Molecular Crystal ◽  
Solid Electrolytes ◽  
Room Temperature ◽  
Molecular Crystals ◽  
Transference Number ◽  
Ion Conducting ◽  
State Ionic

Molecular crystals have attracted increasing attention as a candidate for innovative solid electrolytes with solid-state Mg-ion conductivity. In this work, we synthesized a novel Mg-ion-conducting molecular crystal, Mg{N(SO2CF3)2}2(CH3OC5H9)2 (Mg(TFSA)2(CPME)2), composed of Mg bis(trifluoromethanesulfonyl)amide (Mg(TFSA)2) and cyclopentyl methyl ether (CPME) and elucidated its crystal structure. We found that the obtained Mg(TFSA)2(CPME)2 exhibits solid-state ionic conductivity at room temperature and a high Mg-ion transference number of 0.74. Contrastingly, most Mg-conductive inorganic solid electrolytes require heating above 150–300°C to exhibit ionic conductivity. These results further prove the suitability of molecular crystals as candidates for Mg-ion-conducting solid electrolytes.

Mining Predicted Crystal Structure Landscapes with High Throughput Crystallization: Old Molecules, New Insights

2019 ◽  
Author(s):  
Peng Cui ◽  
David P. McMahon ◽  
Peter Spackman ◽  
Ben M. Alston ◽  
Marc A. Little ◽  
...  
Keyword(s):  
Crystal Structure ◽  
High Throughput ◽  
Structure Prediction ◽  
Organic Molecules ◽  
Screening Method ◽  
Molecular Crystals ◽  
Crystal Structure Prediction ◽  
Tetracarboxylic Acid ◽  
Trimesic Acid ◽  
Interconnected Pores

<a></a><a>Organic molecules tend to close pack to form dense structures when they are crystallized from organic solvents. Porous molecular crystals defy this rule: they typically crystallize with lattice solvent in the interconnected pores. However, the design and discovery of such structures is often challenging and time consuming, in part because it is difficult to predict solvent effects on crystallization. Here, we combine crystal structure prediction (CSP) with a high-throughput crystallization screening method to accelerate the discovery of stable hydrogen-bonded frameworks. We exemplify this strategy by finding new phases of two well-studied molecules in a computationally targeted way. Specifically, we find a new porous polymorph of trimesic acid, δ-<b>TMA</b>, that has a guest free hexagonal pore structure, as well as three new solvent-stabilized diamondoid frameworks</a> of adamantane-1,3,5,7-tetracarboxylic acid (<b>ADTA</b>).

scholarly journals Crystal structure and computational study of an oxo-bridged bis-titanium(III) complex

2021 ◽  
Vol 77 (7) ◽  
Author(s):  
Hannah R. Bloomfield ◽  
Joshua W. Hollett ◽  
Jamie S. Ritch
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Computational Analysis ◽  
Computational Study ◽  
Spin States ◽  
State Structure ◽  
Solid State Structure ◽  
Positional Disorder ◽  
Hartree Fock ◽  
Complex Features

The solid-state structure of the new compound μ-oxido-bis[dichloridotris(tetrahydrofuran-κO)titanium(III)], [Ti2Cl4O(C4H8O)6], at 150 K has been determined. The crystal has monoclinic (C2/c) symmetry and the complex features C 2 symmetry about the bridging O atom. Positional disorder is evident in one of the three tetrahydrofuran environments. A post-Hartree–Fock computational analysis indicates that the complex has nearly degenerate triplet and singlet spin states, with the former favoured slightly by ca 2 kJ mol−1.

Mining Predicted Crystal Structure Landscapes with High Throughput Crystallization: Old Molecules, New Insights

2019 ◽  
Author(s):  
Peng Cui ◽  
David P. McMahon ◽  
Peter Spackman ◽  
Ben M. Alston ◽  
Marc A. Little ◽  
...  
Keyword(s):  
Crystal Structure ◽  
High Throughput ◽  
Structure Prediction ◽  
Organic Molecules ◽  
Screening Method ◽  
Molecular Crystals ◽  
Crystal Structure Prediction ◽  
Tetracarboxylic Acid ◽  
Trimesic Acid ◽  
Interconnected Pores

<a></a><a>Organic molecules tend to close pack to form dense structures when they are crystallized from organic solvents. Porous molecular crystals defy this rule: they typically crystallize with lattice solvent in the interconnected pores. However, the design and discovery of such structures is often challenging and time consuming, in part because it is difficult to predict solvent effects on crystallization. Here, we combine crystal structure prediction (CSP) with a high-throughput crystallization screening method to accelerate the discovery of stable hydrogen-bonded frameworks. We exemplify this strategy by finding new phases of two well-studied molecules in a computationally targeted way. Specifically, we find a new porous polymorph of trimesic acid, δ-<b>TMA</b>, that has a guest free hexagonal pore structure, as well as three new solvent-stabilized diamondoid frameworks</a> of adamantane-1,3,5,7-tetracarboxylic acid (<b>ADTA</b>).

scholarly journals Solid‐State NMR‐Driven Crystal Structure Prediction of Molecular Crystals: The Case of Mebendazole

2021 ◽  
Author(s):  
Federica Bravetti ◽  
Simone Bordignon ◽  
Edith Alig ◽  
Daniel Eisenbeil ◽  
Lothar Fink ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Solid State Nmr ◽  
Structure Prediction ◽  
Molecular Crystals ◽  
Crystal Structure Prediction

Ruthenium(II) Complexes Bearing Thioether-Appended α- Iminopyridine Ligands: Arene Precursors Permit Access to K2-N,N and K3-N,N,S Complexes

2019 ◽  
Author(s):  
Victoria A. Ternes ◽  
Hannah A. Morgan ◽  
Austin P. Lanquist ◽  
Michael P. Murray ◽  
Bradley Wile
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Strong Field ◽  
Active Role ◽  
Binding Mode ◽  
Phenethyl Alcohol ◽  
Ru Complexes

Herein we report the preparation of a series of Ru(II) complexes featuring alpha-iminopyridine ligands bearing thioether functionality (NNS<sup>R</sup>, where R = Me, CH<sub>2</sub>Ph, Ph). Metallation using (<i>p</i> cymene)RuCl dimer permits access to (k<sup>2</sup>-N,N)Ru complexes in which the thioether moiety remains uncoordinated. In the presence of a strong field ligand such as acetonitrile or triphenylphosphine, the p-cymene moiety is displaced, and the ligand adopts a k<sup>3</sup>-N,N,S binding mode. These complexes are characterized using a combination of solution and solid state methods, including the crystal structure of [(NNS<sup>Me</sup>)Ru(NCMe)<sub>2</sub>Cl]Cl. The k<sup>2</sup>-N,N Ru(II) complexes are shown to serve as efficient precatalysts for the oxidation of sec-phenethyl alcohol at 5 mol% loadings, using a variety of external oxidants and solvents. The complex bearing an S-Ph donor was found to be the most active of those surveyed, suggesting that the thioether donor plays an active role in catalyst speciation for this transformation.

Crystal structure of tetraoxa[4]peristylane: Novel CH…O mediated architecture in the solid state

1999 ◽  
Vol 40 (12) ◽  
pp. 2417-2420 ◽  
Author(s):  
Goverdhan Mehta ◽  
Ramdas Vidya ◽  
Kailasam Venkatesan
Keyword(s):  
Crystal Structure ◽  
Solid State

Solid state amorphization of organic molecular crystals using a vibrating mill

1995 ◽  
Vol 94 (12) ◽  
pp. 1013-1018 ◽  
Author(s):  
Itaru Tsukushi ◽  
Osamu Yamamuro ◽  
Takasuke Matsuo
Keyword(s):  
Solid State ◽  
Molecular Crystals ◽  
Organic Molecular Crystals ◽  
State Amorphization
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