Luminescent P-Benzyl Dithienophospholes – A Joint Experimental and Theoretical Investigation

2013 ◽  
Vol 66 (10) ◽  
pp. 1171 ◽  
Author(s):  
Zisu Wang ◽  
Alva Y. Y. Woo ◽  
Thomas Baumgartner
Keyword(s):  
Density Functional Theory ◽  
Single Crystal ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Phenyl Substituent ◽  
Substitution Pattern ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sulfide Species

A series of P-benzyl functionalised dithieno[3,2-b:2′,3′-b]phospholes with different substitution pattern at the phosphorus as well as the conjugated scaffold was synthesised and characterised via optical spectroscopy. Single crystal X-ray crystallography was performed on one species. The experimentally observed data were solidified with density functional theory calculations. In contrast to related benzylated P-phenyl phospholium species, the new systems show pronounced photoluminescence in solution, with the exception of the phosphole sulfide species. The observed photophysics could be explained with dominating π→π* transitions, despite the presence of the benzyl group that had been found to quench the fluorescence in the predecessor benzyl system with P-phenyl substituent.

scholarly journals An 80-Carbon Aromatic Saddle Enabled by a Naphthalene-Directed Scholl Reaction

2020 ◽  
Vol 02 (03) ◽  
pp. 248-252
Author(s):  
Sai Ho Pun ◽  
Chi Kit Chan ◽  
Zhifeng Liu ◽  
Qian Miao
Keyword(s):  
Density Functional Theory ◽  
Single Crystal ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
Negatively Curved

Synthesis of an unprecedented aromatic saddle consisting of 80 sp2 carbons is enabled by including naphthylene groups in the substrate of the Scholl reaction. The negatively curved polycyclic framework of this aromatic saddle is revealed by the single crystal X-ray crystallography, and its stereodynamics are studied with density functional theory calculations.

scholarly journals Synthesis of Chromium(II) Complexes with Chelating Bis(alkoxide) Ligand and Their Reactions with Organoazides and Diazoalkanes

Molecules ◽  
2020 ◽  
Vol 25 (2) ◽  
pp. 273 ◽  
Author(s):  
Sudheer S. Kurup ◽  
Richard J. Staples ◽  
Richard L. Lord ◽  
Stanislav Groysman
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Aryl Azides ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
Chromium Vi ◽  
Imido Complexes ◽  
Structure And Bonding

Synthesis of new chromium(II) complexes with chelating bis(alkoxide) ligand [OO]Ph (H2[OO]Ph = [1,1′:4′,1′’-terphenyl]-2,2′’-diylbis(diphenylmethanol)) and their subsequent reactivity in the context of catalytic production of carbodiimides from azides and isocyanides are described. Two different Cr(II) complexes are obtained, as a function of the crystallization solvent: mononuclear Cr[OO]Ph(THF)2 (in toluene/THF, THF = tetrahydrofuran) and dinuclear Cr2([OO]Ph)2 (in CH2Cl2/THF). The electronic structure and bonding in Cr[OO]Ph(THF)2 were probed by density functional theory calculations. Isolated Cr2([OO]Ph)2 undergoes facile reaction with 4-MeC6H4N3, 4-MeOC6H4N3, or 3,5-Me2C6H3N3 to yield diamagnetic Cr(VI) bis(imido) complexes; a structure of Cr[OO]Ph(N(4-MeC6H4))2 was confirmed by X-ray crystallography. The reaction of Cr2([OO]Ph)2 with bulkier azides N3R (MesN3, AdN3) forms paramagnetic products, formulated as Cr[OO]Ph(NR). The attempted formation of a Cr–alkylidene complex (using N2CPh2) instead forms chromium(VI) bis(diphenylmethylenehydrazido) complex Cr[OO]Ph(NNCPh2)2. Catalytic formation of carbodiimides was investigated for the azide/isocyanide mixtures containing various aryl azides and isocyanides. The formation of carbodiimides was found to depend on the nature of organoazide: whereas bulky mesitylazide led to the formation of carbodiimides with all isocyanides, no carbodiimide formation was observed for 3,5-dimethylphenylazide or 4-methylphenylazide. Treatment of Cr2([OO]Ph)2 or H2[OO]Ph with NO+ leads to the formation of [1,2-b]-dihydroindenofluorene, likely obtained via carbocation-mediated cyclization of the ligand.

Structural assignment of a bis-cyclopentenyl-β-cyanohydrin formedviaalkene metathesis from either a triene or a tetraene precursor

2013 ◽  
Vol 69 (11) ◽  
pp. 1207-1211 ◽  
Author(s):  
Keith G. Andrews ◽  
Christopher S. Frampton ◽  
Alan C. Spivey
Keyword(s):  
Density Functional Theory ◽  
Single Crystal ◽  
Natural Product ◽  
Density Functional ◽  
Major Product ◽  
Functional Theory ◽  
X Ray ◽  
X Ray Crystallography ◽  
Structural Assignment ◽  
Nmr Prediction

The identity of the major product of Ru-catalysed alkene metathesis of two polyene substrates has been determined using density functional theory (DFT) NMR prediction, a1H–1H Total Correlated Spectroscopy (TOCSY) NMR experiment and ultimately by single-crystal X-ray crystallography. The substrates were designed as those that would potentially allow expedient access to thetrans-decalin skeleton of the natural product (−)-euonyminol, but the product was found to be a bis-cyclopentenyl-β-cyanohydrin [1-(1-hydroxycyclopent-3-en-1-yl)cyclopent-3-ene-1-carbonitrile, C11H13NO] rather than thetrans-2,3,6,7-dehydrodecalin-β-cyanohydrin.

scholarly journals Ba3CrN3H: A New Nitride-Hydride with Trigonal Planar Cr4+

2018 ◽  
Author(s):  
Nathaniel W. Falb ◽  
Jennifer N. Neu ◽  
Tiglet Besara ◽  
Jeffrey B. Whalen ◽  
David J. Singh ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Single Crystal ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
Crystal Synthesis

Single crystal synthesis of a new nitride-hydride Ba3CrN3H. X-ray diffraction, nuclear magnetic resonance, and bond-valance sum and density functional theory calculations confirmed the presence and location of the anionic hydrogen in this compound.

scholarly journals Synthesis of dinucleoside acylphosphonites by phosphonodiamidite chemistry and investigation of phosphorus epimerization

2015 ◽  
Vol 11 ◽  
pp. 184-191 ◽  
Author(s):  
William H Hersh
Keyword(s):  
Density Functional Theory ◽  
Single Crystal ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
X Ray Diffraction ◽  
Inversion Barrier ◽  
Functional Theory ◽  
Acyl Chlorides ◽  
X Ray

The reaction of the diamidite, (iPr2N)2PH, with acyl chlorides proceeds with the loss of HCl to give the corresponding acyl diamidites, RC(O)P(N(iPr)2)2 (R = Me (7), Ph (9)), without the intervention of sodium to give a phosphorus anion. The structure of 9 was confirmed by single-crystal X-ray diffraction. The coupling of the diamidites 7 and 9 with 5′-O-DMTr-thymidine was carried out with N-methylimidazolium triflate as the activator to give the monoamidites 3′-O-(P(N(iPr)2)C(O)R)-5′-O-DMTr-thymidine, and further coupling with 3′-O-(tert-butyldimethylsilyl)thymidine was carried out with activation by pyridinium trifluoroacetate/N-methylimidazole. The new dinucleoside acylphosphonites could be further oxidized, hydrolyzed to the H-phosphonates, and sulfurized to give the known mixture of diastereomeric phosphorothioates. The goal of this work was the measurement of the barrier to inversion of the acylphosphonites, which was expected to be low by analogy to the low barrier found in acylphosphines. However, the barrier was found to be high as no epimerization was detected up to 150 °C, and consistent with this, density functional theory calculations give an inversion barrier of over 40 kcal/mol.

scholarly journals Compression behavior of Sm2Ti2O7-pyrochlore up to 50 GPa: single-crystal X-ray diffraction and density functional theory calculations

2014 ◽  
Vol 59 (36) ◽  
pp. 5278-5282 ◽  
Author(s):  
Björn Winkler ◽  
Alexandra Friedrich ◽  
Wolfgang Morgenroth ◽  
Eiken Haussühl ◽  
Victor Milman ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Single Crystal ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
Compression Behavior ◽  
X Ray
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