Optical Rotation of Noncovalent Aggregates

Goldsmith, Michael‐Rock; Jayasuriya, Nilu; Beratan, David N.; Wipf, Peter

doi:10.1021/ja0376893

Cited by 64 publications

(58 citation statements)

References 25 publications

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“…Both scale as the same inverse power of electron-nucleus distance, i.e., ͉r i − R I ͉ −2 , but K n I also depends on R I . The present findings confirm those of the previous paper on H 2 butions are virtually the same, and ͓F , K͑O 1 ͔͒ ones are slightly different on the scale of the plot, defining atomic contributions in the torque scheme. ͓F͑O 1 ͒ , L͔ and ͓F͑O 1 ͒ , K͔ curves are close to one another, but they are characterized by a different pattern with a minimum at conformations in the proximity of ⌽ = −30°.…”

Section: Resultssupporting

confidence: 92%

“…Since its discovery in the beginning of the 19th century it has been used as an experimental tool to measure the enantio purity of chemical compounds. 1 Among the different properties that influence the optical rotatory power ͑ORP͒, several articles have been devoted recently to the effect of the molecular aggregation of the molecule of interest with itself [2][3][4] or with the solvent. [5][6][7] The idea that molecular properties can be rationalized in terms of atomic contributions, transferable from molecule to molecule, constitutes an object of interest from the early days of chemistry.…”

Section: Introductionmentioning

confidence: 99%

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Atomic partition of the optical rotatory power of methylhydroperoxide

Sánchez

Ferraro

Alkorta

et al. 2008

The Journal of Chemical Physics

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Articles you may be interested inOn the determination of the diagonal components of the optical activity tensor in chiral molecules J. Chem. Phys. 140, 074105 (2014) We applied a methodology capable of resolving the optical rotatory power into atomic contributions. The individual atomic contributions to the optical rotatory power and molecular chirality of the methylhydroperoxide are obtained via a canonical transformation of the Hamiltonian by which the electric dipolar moment operator is transformed to the acceleration gauge formalism and the magnetic dipolar moment operator to the torque formalism. The gross atomic isotropic contributions have been evaluated for the carbon, the nonequivalent oxygen, and the nonequivalent hydrogen atoms of methylhydroperoxide, employing a very large Gaussian basis set which is close to the Hartree-Fock limit.

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Section: Resultssupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Atomic partition of the optical rotatory power of methylhydroperoxide

Sánchez

Ferraro

Alkorta

et al. 2008

The Journal of Chemical Physics

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“…Goldsmith et al studied the influence of the dimer formation on the OR of pantolactone. 41 The results were compared with experimental OR as a function of the pantolactone/CCl 4 concentration. The authors found a strong effect of aggregation on OR.…”

Section: Introductionmentioning

confidence: 99%

Conformational behavior of simple furanosides studied by optical rotation

Kaminský¹,

Raich²,

Tomčáková³

et al. 2010

J Comput Chem

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Experimental and theoretical specific optical rotations (OR) of anhydro, epithio, and epiminoderivatives of methyl tetrofuranosides in chloroform solutions have been compared and used as a tool for exploring their conformational behavior. The potential energy surfaces of these saccharides with reduced flexibility were examined with the density functional theory and the MP2 and CCSD(T) wavefunctions methods. Theoretical ORs were obtained by Boltzmann averaging of values calculated for local minima. Resultant rotations could be used to assess the quality of the DFT and MP2 relative conformer energies. OR values calculated for equilibrium geometries in vacuum were significantly improved when the solvent was accounted for by a polarizable continuum model and first and diagonal second OR derivatives were used for an anharmonic vibrational averaging. The DFT used as a default method reproduced the experimental data fairly well. A modified B3LYP functional containing 70% of HF exchange further improved the results. Because of the strong dependence of OR on the conformation, not only the absolute configuration could be determined, but also the conformational populations were estimated. Likewise, the predicted dependence of OR on the light wavelength well agreed with experiment. The increasing precision of the contemporary computational methods thus makes it possible to relate the specific rotation to more detailed features in molecular structure.

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“…A racemic mixture containing equal amounts of right-handed and left-handed forms shows no optical activity. Such structure-property relationship makes optical rotation suitable for versatile applications, ranging from chiral analysis in chemistry, pharmaceutical and biological industries to electro-optical elements12.…”

mentioning

confidence: 99%

Anomalously rotary polarization discovered in homochiral organic ferroelectrics

et al. 2016

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Molecular ferroelectrics are currently an active research topic in the field of ferroelectric materials. As complements or alternatives of conventional inorganic ferroelectrics, they have been designed to realize various novel properties, ranging from multiferroicity and semiconductive ferroelectricity to ferroelectric photovoltaics and ferroelectric luminescence. The stabilizing of ferroelectricity in various systems is owing to the flexible tailorability of the organic components. Here we describe the construction of optically active molecular ferroelectrics by introducing homochiral molecules as polar groups. We find that the ferroelectricity in (R)-(−)-3-hydroxlyquinuclidinium halides is due to the alignment of the homochiral molecules. We observe that both the specific optical rotation and rotatory direction change upon paraelectric-ferroelectric phase transitions, due to the existence of two origins from the molecular chirality and spatial arrangement, whose contributions vary upon the transitions. The optical rotation switching effect may find applications in electro-optical elements.

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Optical Rotation of Noncovalent Aggregates

Cited by 64 publications

References 25 publications

Atomic partition of the optical rotatory power of methylhydroperoxide

Atomic partition of the optical rotatory power of methylhydroperoxide

Conformational behavior of simple furanosides studied by optical rotation

Anomalously rotary polarization discovered in homochiral organic ferroelectrics

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