Probing Charge Delocalization in Solid State Polychromophoric Cation Radicals Using X-ray Crystallography and DFT Calculations

2018 ◽  
Vol 122 (17) ◽  
pp. 9339-9345 ◽  
Author(s):  
Lena V. Ivanova ◽  
Denan Wang ◽  
Sergey Lindeman ◽  
Maxim V. Ivanov ◽  
Rajendra Rathore
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Charge Delocalization ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cation Radicals

scholarly journals Polymorphism in 8-hydroxyquinolin-2(1H)-one by X-ray crystallography, solid-state NMR and DFT calculations

2011 ◽  
Vol 67 (a1) ◽  
pp. C816-C817
Author(s):  
R. M. Claramunt ◽  
M. Á García ◽  
M. Á Farrán ◽  
C. I. Nieto ◽  
M. C. Torralba ◽  
...  
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Solid State Nmr ◽  
X Ray ◽  
X Ray Crystallography

Vicinal-diaryl interactions in stilbenoid hydrocarbons as observed in the through-space charge delocalization of their cation radicals

1999 ◽  
Vol 77 (5-6) ◽  
pp. 913-921 ◽  
Author(s):  
Rajendra Rathore ◽  
Jay K Kochi
Keyword(s):  
Space Charge ◽  
Cation Radical ◽  
Conformational Preference ◽  
Charge Delocalization ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cation Radicals ◽  
Near Ir ◽  
Aromatic Interactions ◽  
Vis Spectroscopy

The conformational preference of vicinal or 1,2-phenyl groups is probed in two classes of ring-substituted 1,2-diphenylbicyclooctene (stilbenoid) hydrocarbons 1a-1d and 2a-2c. UV-vis spectroscopy reveals, and X-ray crystallography verifies, the intramolecular (edge-to-face) orientation for the phenyl-phenyl interaction in stilbenoids 1a-1d. Most importantly, when two pairs of ortho-methyl substituents are present, the cofacial phenyl groups in the stilbenoid donors are established by X-ray crystallography and spectrally observed in the cation radicals (2a+.-2c+.) by the appearance of new bands with strong absorptions in the near IR with λmax = 1100-1315 nm, analogous to those previously observed in intermolecular (aromatic) interactions of aromatic cation radicals.Key words: stilbenoid hydrocarbon, cation radical, aryl-aryl interaction.

Atom Assignment in Solid-State Structures on the Basis of X-ray Crystallography and DFT Calculations – A Case Study on a Molecular Cu–Sb Alloy

2006 ◽  
Vol 2006 (6) ◽  
pp. 1127-1129 ◽  
Author(s):  
Reinhart Ahlrichs ◽  
Dieter Fenske ◽  
Alexander Rothenberger ◽  
Claudia Schrodt ◽  
Stephan Wieber
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
X Ray ◽  
X Ray Crystallography ◽  
Solid State Structures

Two polymorphs of 8-hydroxycarbostyril: X-ray crystallography, solid-state NMR and DFT calculations

2012 ◽  
Vol 1008 ◽  
pp. 88-94 ◽  
Author(s):  
Carla I. Nieto ◽  
M. Ángeles García ◽  
M. Ángeles Farrán ◽  
Rosa M. Claramunt ◽  
M. Carmen Torralba ◽  
...  
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Solid State Nmr ◽  
X Ray ◽  
X Ray Crystallography

scholarly journals Isolation of a chiral anthracene cation radical: X-ray crystallography and computational interrogation of its racemization

2017 ◽  
Vol 53 (18) ◽  
pp. 2748-2751 ◽  
Author(s):  
Maxim V. Ivanov ◽  
Khushabu Thakur ◽  
Anshul Bhatnagar ◽  
Rajendra Rathore
Keyword(s):  
Charge Transfer ◽  
Dft Calculations ◽  
Cation Radical ◽  
Enantioselective Synthesis ◽  
X Ray ◽  
X Ray Crystallography ◽  
Anthracene Derivative ◽  
Cation Radicals ◽  
Radical Salt ◽  
Charge Transfer Materials

Chiral cation-radicals hold significant promise as charge-transfer materials, chiroptical switches, and catalysts for enantioselective synthesis. Herein we identify a chiral anthracene derivative that forms a robust cation-radical salt as established by X-ray crystallography and DFT calculations.

On the importance of antiparallel π–π interactions in the solid state of isatin-based hydrazides

2019 ◽  
Vol 43 (21) ◽  
pp. 8122-8131 ◽  
Author(s):  
Muhammad Naeem Ahmed ◽  
Maryam Arif ◽  
Farah Jabeen ◽  
Haroon Ahmed Khan ◽  
Khawaja Ansar Yasin ◽  
...  
Keyword(s):  
Solid State ◽  
Dft Calculations ◽  
Crystal Structures ◽  
X Ray ◽  
Π Interactions ◽  
X Ray Crystallography ◽  
Isatin Derivatives

Cooperative H-bonding and antiparallel π–π interactions in crystal structures of isatin derivatives are investigated using X-ray crystallography and DFT calculations.

Structure and wavelength modification in retinylidene iminium salts

1996 ◽  
Vol 74 (4) ◽  
pp. 591-601 ◽  
Author(s):  
George R. Elia ◽  
Ronald F. Childs ◽  
James F. Britten ◽  
Daniel S.C. Yang ◽  
Bernard D. Santarsiero
Keyword(s):  
Solid State ◽  
Alkyl Substituent ◽  
Spectroscopic Properties ◽  
Crystal Lattices ◽  
Charge Delocalization ◽  
X Ray ◽  
X Ray Crystallography ◽  
Iminium Salts ◽  
Internuclear Distances ◽  
Relationship Of

The spectroscopic and structural properties of the perchlorate and triflate salts of N-n-butyl-retinylidene imine, 2 and 3, have been examined in solution and solid phases. In solution these salts were found to exhibit very similar UV and NMR spectroscopic properties. However, in the solid state marked differences in their absorption spectra (2, λmax = 504 nm; 3, λmax = 445 nm) and 13C NMR spectra were found. The structures of the two salts were determined by X-ray crystallography. The cations in each of the salts were shown to have very similar conformations, detailed structures, and packing in their crystal lattices. The differences in the spectroscopic properties of the salts in the solid state could not be accounted for on the basis of any structural differences in the cations themselves. In terms of cation–anion interactions, a strong hydrogen bonding interaction was found in each case between the N-H proton and an oxygen atom of the counterion. However, there were significant differences between the two salts in terms of the [Formula: see text] internuclear distances (2, [Formula: see text] and in 3, 2.85(1) Å). The results are strongly suggestive that the wavelength and positive charge delocalization in retinylidène iminium salts are controlled by variation of the distance between the anion and the proton bonded to the Schiff base nitrogen atom. The work reported here represents the first examples of secondary retinylidene iminium salts containing an N-alkyl substituent to be successfully analyzed by X-ray crystallography. The relationship of these observations in the solid state to the spectroscopic properties of the natural visual pigments is explored. Key words: retinylidène iminium salts, iminium salts, cation–anion interactions.

Solid-state and gas-phase structures of two conformers of N-(4-methylphenyl)-N′,N′′-bis(morpholinyl) phosphoric triamide; insights from X-ray crystallography and DFT calculations

2011 ◽  
Vol 67 (3) ◽  
pp. 238-243 ◽  
Author(s):  
Khodayar Gholivand ◽  
Hamid Reza Mahzouni
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Dft Calculations ◽  
Gas Phase ◽  
Bond Critical Point ◽  
X Ray ◽  
X Ray Crystallography ◽  
Equal Chance ◽  
Phosphoric Triamide ◽  
Hydrogen Bonded

A phosphoric triamide with the formula (4-CH3—C6H4NH)P(O)(NC4H8O)2 has been synthesized and characterized. X-ray crystallography at 120 K reveals that the title compound is composed of two symmetrically independent molecules in the solid state. Density functional theory (DFT) calculations reveal that two conformers A and B are very close to each other from an energy point of view. Thus there is equal chance that the presence of two conformers in the lattice may lead to hydrogen-bonded chains with an ABABAB arrangement. Hydrogen bonds of the type OP...H—N (OP being the phosphoryl O atom) are established between the two conformers with binding energies of −18.8 and −20.3 kJ mol−1 (at B3LYP/6–31+G*). The electronic delocalization LP(OP) → σ*(N—H), LP(OP) being the lone pair of OP, leads to a decrease in the strength of the N—H bond during hydrogen bonding between the conformers. The charge density (ρ) at the bond critical point (b.c.p.) of N—H decreases by ∼ 0.012–0.014 e Å–3 when the molecule participates in hydrogen bonding. This may explain the red shift of the ν(N—H) stretching frequency from a single molecule in the gas phase to a hydrogen-bonded one in the solid state.

scholarly journals A Mixed-metal Mixed-halide Complex Prepared from Zerovalent Copper and Lead Salts: Solution and Solid-state Chemistry

1999 ◽  
Vol 23 (11) ◽  
pp. 670-671
Author(s):  
Larisa A. Kovbasyuk ◽  
Olga Yu. Vassilyeva ◽  
Vladimir N. Kokozay ◽  
Wolfgang Linert ◽  
Paul R. Raithby
Keyword(s):  
Solid State ◽  
Direct Interaction ◽  
Solid State Chemistry ◽  
X Ray ◽  
Mixed Metal ◽  
X Ray Crystallography ◽  
Halide Complex ◽  
Layer Arrangement ◽  
Lead Salts

The mixed-metal mixed-halide complex [CuPbBrlL2]2 has been prepared by the direct interaction of zerovalent copper with lead halides and 2-dimethylaminoethanol (HL) in dmso and has been characterized by X-ray crystallography; the structure shows a layer arrangement of the tetranuclear metal units through the μ3-halogen bridging.

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