Solvent Effect on the Photophysical Properties of Terpyridine Incorporating Pyrene Moiety: Estimation of Dipole Moments by Solvatochromic Shift Methods.

The absorption and fluorescence emission spectra of terpyridine incorporating pyrene moiety (Tpy-pyr) have been recorded in extensive variety of solvents having different polarities. The effect of the solvent on the spectral characteristics are examined. It is shown that Tpy-pyr exhibit positive solvatochromism, large Stokes shift values in polar solvents, and fluorescence in the long wavelength region of the visible range.

Distinctive tunable photophysical properties of versatile environmentally-sensitive tribranched cyanopyridine fluorophores.

In the present work, twenty-four environmentally-sensitive cyanopyridine fluorophores bearing pyrene and/ or fluorene with different para-substituted-phenyl moieties that have been previously designed and synthesized by us are studied in depth for their photophysical properties. Initially, the optical performances of the compounds were investigated by employing UV-visible and fluorescence spectroscopic tools in various aprotic and protic solvents. All the compounds exhibited absorption bands between 310 and 452 nm, and emission bands between 454 and 633 nm.

Unprecedented Regio- and Stereoselective Synthesis of Pyrene-Grafted Dispiro[indoline-3,2'-pyrrolidine-3',3″-indolines]: Expedient Experimental and Theoretical Insights into Polar [3 + 2] Cycloaddition.

A series of dispiro[indoline-3,2'-pyrrolidine-3',3″-indolines] was synthesized via a multicomponent polar [3 + 2] cycloaddition (32CA) reaction of isatin derivatives, sarcosine and ()-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-one derivatives. The regio- and stereochemistries of the cycloadducts were established on the basis of one-dimensional (1D) (H-, C-, C-CRAPT NMR) and two-dimensional (2D) homonuclear and heteronuclear correlation NMR spectrometry experiments (H-H gDQFCOSY, C-H-HSQCAD, C-H-HMBCAD, H-H-ROESYAD). The molecular mechanism and regio- and stereoselectivities of the cycloaddition (CA) reaction have been investigated utilizing a density functional theory (DFT) method and were thoroughly explained based on the transition-state stabilities and global/local electrophilicity/nucleophilicity reactivity indices of the reactants.

Exploiting a multicomponent domino reaction strategy for the tailoring of versatile environmentally sensitive fluorophore-based nicotinonitriles incorporating pyrene and fluorene moieties.

A simplistic and highly effective protocol for the synthesis of a new class of poly-functionalized innovative nicotinonitriles incorporating pyrene and/or fluorene moieties has been developed through the domino four-component condensation reaction of 1-(pyren-1-yl)ethanone/1-(9-fluoren-2-yl)ethanone, numerous aromatic aldehydes, and 3-oxo-3-(pyren-1-yl)propanenitrile/3-(9-fluoren-2-yl)-3-oxopropanenitrile and ammonium acetate in acetic acid as a reaction medium. The advantages of this approach are the short reaction time, excellent yield, and the easy experimental workup that affords substrate diversity and operative competence under metal-free reaction conditions for the formation of C-C and C-N bonds. The substituent effects on the photophysical property-based absorption and the emission of the synthesized compounds in dichloromethane have been well-investigated.

Facile access to regio- and stereoselective synthesis of highly functionalized spiro[indoline-3,2'-pyrrolidines] incorporating a pyrene moiety: experimental, photophysical and theoretical approach.

The regio- and stereochemical polar [3 + 2] cycloaddition of azomethine ylides, which were generated by the reaction of isatin and sarcosine or benzylamine, with ()-3-aryl-1-(pyren-1-yl)prop-2-en-1-ones as dipolarophiles, was studied using experimental and theoretical methods. The chemical structures and relative configurations of all products have been fully established by 1D and 2D homonuclear and heteronuclear correlation NMR spectrometry. The effects of the electronic and steric factors of the reactions were discussed.

Electronic and solvent effects on kinetics of SAr substitution reactions of substituted anilines with 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole in MeOH-MeSO mixtures of varying composition: one reaction with two mechanistic pathways.

Abstract: The kinetics and mechanism of the aromatic nucleophilic substitution reactions of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole with -X-substituted anilines (X = OH, OMe, Me, H, F, I, Cl) were studied in MeOH-MeSO mixtures and pure MeSO at 25.0 °C. The second-order rate coefficients depend on the substitutent in aniline and give good Hammett and Brønsted correlations; a polar SAr reaction is proposed for the reaction in different MeOH-MeSO mixtures.

The Diels-Alder reaction of 4,6-dinitrobenzofuroxan with 1-trimethylsilyloxybuta-1,3-diene: a case example of a stepwise cycloaddition.

The reaction of 4,6-dinitrobenzofuroxan (DNBF) with 1-trimethylsilyloxybuta-1,3-diene (8) is shown to afford a mixture of [2+4] diastereomeric cycloadducts (10, 11) through stepwise addition-cyclization pathways. Zwitterionic intermediate sigma-adduct 9, which is involved in the processes, has been successfully characterized by (1)H and (13)C NMR spectroscopy and UV/visible spectrophotometry in acetonitrile. A kinetic study has been carried out in this solvent that revealed that the rate of formation of 9 nicely fits the three-parameter equation log k=s(E+N) developed by Mayr to describe the feasibility of nucleophile-electrophile combinations.

The ambident reactivity of 2,4,6-tris(trifluoromethanesulfonyl)anisole in methanol: using the SO2CF3 group as a tool to reach the superelectrophilic dimension in sigma-complexation processes.

The kinetics of sigma complexation of 2,4,6-tris(trifluoromethanesulfonyl)anisole (7 d) have been investigated over a large pH range of 2-13.70 at T = 20 degrees C in methanol. Two competitive processes associated with the initial addition of MeO(-) at the unsubstituted 3-position of 7 d to give a 1,3-dimethoxy adduct (9 d-Me) and a subsequent and slow conversion of this species into a 1,1-dimethoxy isomer (8 d-Me) have been identified.

Electrophilicity of aromatic triflones in sigma-complexation processes.

The kinetics of sigma-complexation of 2,6-bis(trifluoromethanesulfonyl)-4-nitroanisole (4) have been investigated over a large pH range of 2-15.68 in methanol. Two competitive processes have been identified with the initial addition of MeO(-) at the unsubstituted 3-position of 4 to give a 1,3-dimethoxy adduct (4b-Me) and a subsequent and slow conversion of this species into the 1,1-dimethoxy isomer (4a-Me).