A synthetic co-crystal prepared by cooperative single-crystal-to-single-crystal solid-state Diels–Alder reaction

2017 ◽  
Vol 53 (36) ◽  
pp. 4969-4972 ◽  
Author(s):  
S. Khorasani ◽  
M. A. Fernandes
Keyword(s):  
Charge Transfer ◽  
Solid State ◽  
Single Crystal ◽  
Charge Transfer Complex ◽  
Alder Reaction ◽  
Diels Alder ◽  
Energy Calculations ◽  
Diels Alder Reaction ◽  
Close Contacts

Solid-state Diels–Alder reaction in a 2 : 1 donor to acceptor charge-transfer complex leads to a synthetic co-crystal composed of product and unreacted donor. Analysis of close contacts and DFT energy calculations indicate that the reaction occurs cooperatively where the arrangement of molecules shown in (ii) is favoured.

scholarly journals Cooperativity in the Reaction of 9-Methylanthracene With a 1,4-Dithiin Molecule

2014 ◽  
Vol 70 (a1) ◽  
pp. C913-C913
Author(s):  
Sanaz Khorasani ◽  
Manuel Fernandes
Keyword(s):  
Charge Transfer ◽  
Solid State ◽  
Single Crystal ◽  
Lattice Energy ◽  
Alder Reaction ◽  
Diels Alder ◽  
Reaction Products ◽  
X Ray Diffraction ◽  
X Ray ◽  
Diels Alder Reaction

Solid-state chemistry involves the manipulation of molecules and materials through photochemical, thermal, or mechanical reaction methods. Single-crystal-to-single-crystal (SCSC) reactions are rare, but offer the opportunity to study reaction mechanisms and molecular motions in the solid state at the atomic level using single crystal X-ray diffraction. This allows the effect of the surrounding molecules, and hence the reaction cavity, on the reacting molecules to be examined which may ultimately lead to postcrystallization methods for creating new materials or reaction products that cannot easily be obtained via solution. SCSC reactions involving two different molecules are relatively uncommon. A convenient system that allows the study of such reactions is the [4+2] Diels-Alder reaction of 1,4-dithiintetracarboxylic type compounds with anthracene derivatives. In the work reported here, electron donor to acceptor interactions between 9-Methylanthracene and bis(N-cyclobutylimino)-1,4-dithiin lead to the formation of chiral charge transfer (CT) crystals [1]. These undergo a topochemical thermal SCSC [4 + 2] Diels-Alder reaction in the solid state. CT crystals were reacted at 400C, their structures determined by X-ray diffraction at various degrees of conversion, and examined using Hirshfeld surfaces and lattice energy calculations to find evidence of reaction cooperativity and feedback mechanisms. In this case, a maximum reaction conversion of around 96% was obtained indicating that the reaction is non-random within the charge transfer stacks, with close contacts between product molecules in the reacted crystal also providing some evidence for reaction cooperativity along the b axis perpendicular to the CT stacking axis.

Positive Photocatalysis of a Diels−Alder Reaction by Quenching of Excited Naphthalene−Indole Charge-Transfer Complex with Cyclohexadiene

2007 ◽  
Vol 9 (3) ◽  
pp. 453-456 ◽  
Author(s):  
María González-Béjar ◽  
Salah-Eddine Stiriba ◽  
Miguel A. Miranda ◽  
Julia Pérez-Prieto
Keyword(s):  
Charge Transfer ◽  
Charge Transfer Complex ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

scholarly journals A single-crystal-to-single-crystal Diels–Alder reaction with mixed topochemical and topotactic behaviour

CrystEngComm ◽  
2015 ◽  
Vol 17 (46) ◽  
pp. 8933-8945 ◽  
Author(s):  
S. Khorasani ◽  
D. S. Botes ◽  
M. A. Fernandes ◽  
D. C. Levendis
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Conformational Change ◽  
Weak Interactions ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

During a SCSC solid-state Diels–Alder reaction, voids are created, followed by conformational change and crystal annealing that lead to the formation of new weak interactions.

scholarly journals On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.

2021 ◽  
Author(s):  
Andrés Henao Aristizàbal ◽  
Yomna Gohar ◽  
René Whilhelm ◽  
Thomas D. Kühne
Keyword(s):  
Hydrogen Bond ◽  
Free Energy ◽  
Charge Transfer ◽  
Hydrogen Bonds ◽  
Density Functional ◽  
Alder Reaction ◽  
Free Energy Calculations ◽  
Diels Alder ◽  
Diels Alder Reaction

Accelerated chemistry at the interface with water has received increasing attention. The mechanisms behind the enhanced reactivity On-Water are not yet clear. In this work we use a Langevin scheme in the spirit of second generation Car-Parrinello to accelerate the second-order density functional Tight-Binding (DFTB2) method in order to investigate the free energy of two Diels-Alder reaction On-Water: the cycloaddition between cyclopentadiene and ethyl cinnamate or thionocinnamate. The only difference between the reactants is the substitution of a carbonyl oxygen for a thiocarbonyl sulfur, making possible the distinction between them as strong and weak hydrogen-bond acceptors. We find a different mechanism for the reaction during the transition states and uncover the role of hydrogen bonds along with the reaction path. Our results suggest that acceleration of Diels-Alder reactions do not arise from an increased number of hydrogen bonds at the transition state and charge transfer plays a significant role. However, the presence of water and hydrogen-bonds is determinant for the catalysis of these reactions.

Diels‐Alder reaction rate in the solid state and the evidence of the location of molecular complexes between the reagents on the reaction pathway

2020 ◽  
Vol 53 (2) ◽  
pp. 207-212
Author(s):  
Vladimir D. Kiselev ◽  
Anastasia O. Kolesnikova ◽  
Ildar F. Dinikaev ◽  
Alexey A. Shulyatiev ◽  
Alexander E. Klimovitskii ◽  
...  
Keyword(s):  
Solid State ◽  
Reaction Rate ◽  
Reaction Pathway ◽  
Molecular Complexes ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction

Diels-Alder reaction volumes in the solid state and solution

2004 ◽  
Vol 53 (11) ◽  
pp. 2490-2495 ◽  
Author(s):  
V. D. Kiselev ◽  
G. G. Iskhakova ◽  
E. A. Kashaeva ◽  
L. N. Potapova ◽  
A. I. Konovalov
Keyword(s):  
Solid State ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Reaction Volumes
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