Extension and Application of Excited-State Constants of &lt;i&gt;meta&lt;/i&gt;-Substituents

Zhu, Qian; Cao, Chao‐Tun; Cao, Chenzhong

doi:10.3866/pku.whxb201611291

Cited by 12 publications

(16 citation statements)

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“…For the convenience of the readers, we collected the existing

σ_{CC}^{ex}

values of para‐/meta‐substituent reported by previous studies and the

σ_{CC ((), p)}^{ex}

values of Table and listed them in Table . Also, we plotted the

σ_{CC}^{ex}

of substituents in Table against σ of the corresponding substituents (see Figure ).…”

Section: Results Discussionmentioning

confidence: 99%

“…

σ_{CC ((), m)}^{ex}

is the excited‐state substituent constant of meta‐substituent. The

σ_{CC ((), m)}^{ex}

values of OMe, Me, F, Cl, CF 3 , and CN were taken from Cao et al The

σ_{CC ((), m)}^{ex}

values of OH were taken from Zhou et al The

σ_{CC ((), m)}^{ex}

values of NO 2 , I, CHCH 2 , Ph, Et, NMe 2 , and CCH were taken from Zhu et al…”

Section: Results Discussionmentioning

confidence: 99%

“…Cao et al investigated systematically the ν max of UV absorption for stilbene compounds (XSBY) and established a correlation equation. Recently, we further synthesized 7 series of stilbene compounds and collected the ν max values of disubstituted benzene (XArY) and XSBY and got the ν max values of total 225 compounds. Then we correlated the ν max with 3 parameters ( σ (XY),

σ_{CC}^{ex}

, and ν max,parent ) and obtained Equation .…”

Section: Determining the σCc()pex Values Of Furyl And Thienylmentioning

confidence: 99%

“…Above situation is due to the difficulties of the synthesis of organic compounds and the establishment of model equations. Therefore, if we want to increase

σ_{CC}^{ex}

values of certain groups, we have to do more experiments . As we know, furyl and thienyl are common optically active groups and appear more frequently in organic compounds, and the extraction of their

σ_{CC}^{ex}

is an important work for the study of optical materials.…”

Section: Introductionmentioning

confidence: 99%

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Determining the excited‐state substituent constants of furyl and thienyl groups

Cao

2018

J of Physical Organic Chem

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Six series of styrene derivatives XCH═CHArY (total of 65) containing the styrene parent molecular skeleton were synthesized (here, Y is OMe, Me, H, F, Cl, CF3, CN, and NO2, and X is 2‐furyl, 3‐furyl, 2′‐methyl‐2‐furyl, 2‐thienyl, 3‐thienyl, and 2′‐methyl‐2‐theniyl). Their ultraviolet absorption spectra were measured in anhydrous ethanol, and their wavelength of absorption maximum λmax was recorded. For the wavenumber νmax (cm−1, νmax = 1/λmax) of the obtained λmax, a quantitative correlation analysis was performed, and 6 excited‐state substituent constants σCC()pex of groups X were obtained by means of curve‐fitting method. Taking the νmax values of total 90 compounds of styrene derivatives as a data set (including 25 compounds from reference and 65 compounds of this work), a quantitative correlation analysis was performed, and the reliability of the obtained σCC()pex was verified. In addition, 12 samples of disubstituted Schiff bases (XCH═NArY) involving the above groups X were synthesized, and their νmax values were recorded. Using these 12 νmax together with the 14 νmax values of Schiff bases taken from reference (total of 26 compounds), it was further verified that the σCC()pex values are reliable by means of quantitative correlation method.

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“…For the convenience of the readers, we collected the existing

σ_{CC}^{ex}

values of para‐/meta‐substituent reported by previous studies and the

σ_{CC ((), p)}^{ex}

values of Table and listed them in Table . Also, we plotted the

σ_{CC}^{ex}

of substituents in Table against σ of the corresponding substituents (see Figure ).…”

Section: Results Discussionmentioning

confidence: 99%

“…

σ_{CC ((), m)}^{ex}

is the excited‐state substituent constant of meta‐substituent. The

σ_{CC ((), m)}^{ex}

values of OMe, Me, F, Cl, CF 3 , and CN were taken from Cao et al The

σ_{CC ((), m)}^{ex}

values of OH were taken from Zhou et al The

σ_{CC ((), m)}^{ex}

values of NO 2 , I, CHCH 2 , Ph, Et, NMe 2 , and CCH were taken from Zhu et al…”

Section: Results Discussionmentioning

confidence: 99%

σ_{CC}^{ex}

, and ν max,parent ) and obtained Equation .…”

Section: Determining the σCc()pex Values Of Furyl And Thienylmentioning

confidence: 99%

“…Above situation is due to the difficulties of the synthesis of organic compounds and the establishment of model equations. Therefore, if we want to increase

σ_{CC}^{ex}

σ_{CC}^{ex}

is an important work for the study of optical materials.…”

Section: Introductionmentioning

confidence: 99%

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Determining the excited‐state substituent constants of furyl and thienyl groups

Cao

2018

J of Physical Organic Chem

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“…To quantify the effect of substituent on the UV spectra of organic compounds, author's group proposed excited‐state substituent constant

σ_{CC}^{ex}

. Using the

σ_{CC}^{ex}

constant together with Hammett electronic effect constant σ, the wavenumbers ν max of the λ max were well correlated for these conjugated compounds involving substituted stilbenes and benzenes, styrene derivatives, aryl Schiff bases, and disubstituted pyrimidines . Here, we also employed the excited‐state substituent constant

σ_{CC}^{ex}

and Hammett electronic effect constant σ to quantify the Δν WSL of MC‐AgNPs solutions.…”

Section: Resultsmentioning

confidence: 99%

Effect of substituents on the UV spectra of supermolecular system: Silver nanoparticles with bi‐aryl Schiff bases containing hydroxyl

Cao

Cheng

Zhang

et al. 2018

J of Physical Organic Chem

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Effect of substituents on the ultraviolet (UV) spectra of supermolecular system involving silver nanoparticles (AgNPs) and Schiff bases was investigated. AgNPs and 49 samples of model compounds (MC), bi-aryl Schiff bases containing hydroxyl (XBAY, involving 4-OHArCH¼NArY, 2-OHArCH¼NArY, XArCH¼NAr-4′-OH, and XArCH¼NAr-2′-OH), were synthesized. The size of AgNPs was characterized by transmission electron microscopy (TEM), and the UV absorption spectra of AgNPs, XBAYs, and MC-AgNPs mixed solutions were measured, respectively. The results show that (1) the size of AgNPs is larger in MC-AgNPs solutions than that in AgNPs solution due to the distribution of MC molecules on the surface of AgNPs; (2) the UV absorption wavelength of XBAYs changes in the action of AgNPs and their wavelength shift exists limitation between XBAY and MC-AgNPs solutions; and (3) the wavelength shift limit of MC-AgNPs (λ WSL ) is influenced by the substituents X and Y and the position of hydroxyl OH. The wavenumber Δν WSL of λ WSL can be quantified by employing the excited-state substituent constant σ ex CC and Hammett constant σ of substituents X and Y. Comparing with the 4-OH, the 4′-OH makes the Δν WSL a red shift, whereas the 2′-OH, comparing with the 2-OH, makes the Δν WSL a blue shift.

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Influences of polarizability effect of alkyl group and homoring competition effect of substituents on the NMR spectra of salen‐type Schiff base

Wei¹,

Cao²

2021

Magnetic Reson in Chemistry

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Salen-type Schiff bases are a kind of important compounds and are widely used. In order to explore the effect of alkyl groups and substituents attached to aromatic ring on the chemical shifts, 63 title compounds were synthesized.Their 1 H NMR and 13 C NMR spectra were obtained; and the effects of the alkyl chain length and substituents on the chemical shifts (δ H (CH N), δ C (CH N), δ H (OH), and δ C (C OH)) were studied. The results show that (1) the alkyl polarizability effect index (PEI) has an important influence on the chemical shifts of the above four atoms, with the increase of PEI, the values of δ H (CH N) and δc(CH N) decrease, and the values of δ H (OH) and δ C (C OH) increase. (2) The influence of substituent X attached to aromatic ring on the chemical shift is related to its position by taking OH or CH N as reference. As for the effect of substituent on the chemical shifts, the effect of Hammett constant σ(X) OH and excited-state substituent parameter σ ex CC X ð Þ OH with OH as reference are different from that ofσ(X) CH N and σ ex CC X ð Þ CH N with CH N as reference, and there is a "homoring competition effect" of the substituent.(3) The effect of the cross-interaction between X and OH on the chemical shift is also significantly different due to the different position of X. Quantitative correlation equations against chemical shifts were built for the four atoms, and the stability and prediction ability of the obtained equations were confirmed by leave-one-out cross validation.

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Extension and Application of Excited-State Constants of <i>meta</i>-Substituents

Cited by 12 publications

References 0 publications

Determining the excited‐state substituent constants of furyl and thienyl groups

Determining the excited‐state substituent constants of furyl and thienyl groups

Effect of substituents on the UV spectra of supermolecular system: Silver nanoparticles with bi‐aryl Schiff bases containing hydroxyl

Influences of polarizability effect of alkyl group and homoring competition effect of substituents on the NMR spectra of salen‐type Schiff base

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