Correlation of Intermolecular Acyl Transfer Reactivity with Noncovalent Lattice Interactions in Molecular Crystals: Toward Prediction of Reactivity of Organic Molecules in the Solid State

2018 ◽  
Vol 83 (7) ◽  
pp. 3952-3959 ◽  
Author(s):  
Shobhana Krishnaswamy ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Organic Molecules ◽  
Molecular Crystals ◽  
Acyl Transfer

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.

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

Theoretical Investigation of Polymorph- and Coformer-Dependent Photoluminescence in Molecular Crystals

CrystEngComm ◽  
2021 ◽  
Author(s):  
Xibo Feng ◽  
Axel D. Becke ◽  
Erin R. Johnson
Keyword(s):  
Solid State ◽  
Theoretical Investigation ◽  
Molecular Crystals ◽  
Research Interest

Polymorph- and coformer-dependent photoluminescence (PL) are among the variety of novel solid-state PL phenomena recently observed in many molecular crystals. They are of particular research interest due to their direct...

Aggregation-induced emission in precursors to porous molecular crystals

2017 ◽  
Vol 53 (72) ◽  
pp. 10022-10025 ◽  
Author(s):  
Zhenglin Zhang ◽  
Mohamed I. Hashim ◽  
Ognjen Š. Miljanić
Keyword(s):  
Solid State ◽  
Molecular Crystals ◽  
Aggregation Induced Emission ◽  
Emission Behavior ◽  
Solid State Fluorescence

Trigonal fluorinated pyrazoles assemble into porous molecular crystals and show solid-state fluorescence. However, their emission behavior in solution is dramatically different.

Correlation of the solid-state reactivities of racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate and its 4,4′-bipyridine cocrystal with their crystal structures

2014 ◽  
Vol 70 (11) ◽  
pp. 1040-1045 ◽  
Author(s):  
Majid I. Tamboli ◽  
Vir Bahadur ◽  
Rajesh G. Gonnade ◽  
Mysore S. Shashidhar
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Transfer Reaction ◽  
Acyl Transfer ◽  
Transfer Reactions ◽  
Group Transfer ◽  
Hydrogen Bonding Interactions ◽  
Benzoyl Group ◽  
The Stability ◽  
Group Migration

Racemic 2,4(6)-di-O-benzoyl-myo-inositol 1,3,5-orthoformate, C21H18O8,(1), shows a very efficient intermolecular benzoyl-group migration reaction in its crystals. However, the presence of 4,4′-bipyridine molecules in its cocrystal, C21H18O8·C10H8N2,(1)·BP, inhibits the intermolecular benzoyl-group transfer reaction. In(1), molecules are assembled around the crystallographic twofold screw axis (baxis) to form a helical self-assembly through conventional O—H...O hydrogen-bonding interactions. This helical association places the reactive C6-O-benzoyl group (electrophile, El) and the C4-hydroxy group (nucleophile, Nu) in proximity, with a preorganized El...Nu geometry favourable for the acyl transfer reaction. In the cocrystal(1)·BP, the dibenzoate and bipyridine molecules are arranged alternately through O—H...N interactions. The presence of the bipyridine molecules perturbs the regular helical assembly of the dibenzoate molecules and thus restricts the solid-state reactivity. Hence, unlike the parent dibenzoate crystals, the cocrystals do not exhibit benzoyl-transfer reactions. This approach is useful for increasing the stability of small molecules in the crystalline state and could find application in the design of functional solids.

scholarly journals Predicting the structures and associated phase transition mechanisms in disordered crystals via a combination of experimental and theoretical methods

2018 ◽  
Vol 211 ◽  
pp. 425-439 ◽  
Author(s):  
Michael T. Ruggiero ◽  
Johanna Kölbel ◽  
Qi Li ◽  
J. Axel Zeitler
Keyword(s):  
Phase Transition ◽  
Solid State ◽  
Time Domain ◽  
Density Functional ◽  
Molecular Crystals ◽  
Terahertz Time Domain Spectroscopy ◽  
Functional Theory ◽  
Theoretical Methods ◽  
Dynamics Simulations ◽  
Transformation Processes

Experimental terahertz time-domain spectroscopy and theoretical solid-state ab initio density functional theory and molecular dynamics simulations are used to elucidate the structures, dynamics, and phase transformation processes of molecular crystals undergoing a solid-state order–disorder transition.

scholarly journals Two-dimensional inorganic molecular crystals

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Wei Han ◽  
Pu Huang ◽  
Liang Li ◽  
Fakun Wang ◽  
Peng Luo ◽  
...  
Keyword(s):  
Organic Molecules ◽  
Electronic Devices ◽  
Molecular Crystals ◽  
High Energy ◽  
Two Dimensional ◽  
Β Phase ◽  
Α Phase ◽  
Growth Plane ◽  
Transmission Electron

Abstract Two-dimensional molecular crystals, consisting of zero-dimensional molecules, are very appealing due to their novel physical properties. However, they are mostly limited to organic molecules. The synthesis of inorganic version of two-dimensional molecular crystals is still a challenge due to the difficulties in controlling the crystal phase and growth plane. Here, we design a passivator-assisted vapor deposition method for the growth of two-dimensional Sb2O3 inorganic molecular crystals as thin as monolayer. The passivator can prevent the heterophase nucleation and suppress the growth of low-energy planes, and enable the molecule-by-molecule lateral growth along high-energy planes. Using Raman spectroscopy and in situ transmission electron microscopy, we show that the insulating α-phase of Sb2O3 flakes can be transformed into semiconducting β-phase under heat and electron-beam irradiation. Our findings can be extended to the controlled growth of other two-dimensional inorganic molecular crystals and open up opportunities for potential molecular electronic devices.

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