Dataset Information

Nitro-Substituted Dipyrrolyldiketone BF₂ Complexes as Electronic-State-Adjustable Anion-Responsive ?-Electronic Systems.

ABSTRACT: Nitro-substituted ?-electronic molecules are fascinating because of their unique electronic and optical properties and the ease of their transformation into various functional derivatives. Herein, nitro-introduced dipyrrolyldiketone BF₂ complexes as anion-responsive ?-electronic molecules were synthesized, and their electronic properties and anion-binding abilities were investigated by spectroscopic analyses and theoretical studies. The obtained nitro-substituted derivatives showed solvent-dependent UV/vis spectral changes and high anion-binding affinities due to the easily pyrrole-inverted conformations and polarized pyrrole NH sites upon the introduction of electron-withdrawing moieties.

SUBMITTER: Kuno A

PROVIDER: S-EPMC7866090 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Nitro-Substituted Dipyrrolyldiketone BF<sub>2</sub> Complexes as Electronic-State-Adjustable Anion-Responsive π-Electronic Systems.

Kuno Atsuko A Maeda Hiromitsu H

Molecules (Basel, Switzerland) 20210123 3

Nitro-substituted π-electronic molecules are fascinating because of their unique electronic and optical properties and the ease of their transformation into various functional derivatives. Herein, nitro-introduced dipyrrolyldiketone BF<sub>2</sub> complexes as anion-responsive π-electronic molecules were synthesized, and their electronic properties and anion-binding abilities were investigated by spectroscopic analyses and theoretical studies. The obtained nitro-substituted derivatives showed so ...[more]

PMID: 33498695

Similar Datasets

Project description:The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and the PARACEST spectra of the complex.

Dataset Information

Nitro-Substituted Dipyrrolyldiketone BF₂ Complexes as Electronic-State-Adjustable Anion-Responsive ?-Electronic Systems.

Publications

Nitro-Substituted Dipyrrolyldiketone BF<sub>2</sub> Complexes as Electronic-State-Adjustable Anion-Responsive π-Electronic Systems.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Dataset Information

Nitro-Substituted Dipyrrolyldiketone BF2 Complexes as Electronic-State-Adjustable Anion-Responsive ?-Electronic Systems.

Publications

Nitro-Substituted Dipyrrolyldiketone BF<sub>2</sub> Complexes as Electronic-State-Adjustable Anion-Responsive π-Electronic Systems.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Nitro-Substituted Dipyrrolyldiketone BF₂ Complexes as Electronic-State-Adjustable Anion-Responsive ?-Electronic Systems.