Electron-donating Ability Of Substituents Research Articles

Self-Sensitized and Reversible O2 Reactivity with Bisphenalenyls for Simple, Tunable, and Multicycle Colorimetric Oxygen-Sensing Films.

Monitoring the levels of molecular oxygen (O2) is critical for numerous applications, but there is still a long-standing challenge to develop robust and cost-effective colorimetric sensors that enable detection by changes in color. Current technologies employ chromophores that require additional additives, which inherently increase the cost and complexity. Here, we report that bisphenalenyls (PQPLs) function as the single active component for colorimetric O2 sensing through their quantitative conversion into aromatic endoperoxides (EPOs). PQPLs display self-sensitizing reactivity: they are capable of generating singlet oxygen and binding it without the need for external photosensitizers. The rates of PQPL photooxygenation depend on the electron-donating ability of substituents, which highlights a simple strategy for tuning O2 sensitivity. EPOs are stable under ambient conditions but can be thermally stimulated to convert back to PQPLs and concomitantly release O2. Polymer-supported (PTMSP) films of PQPLs (2 wt %) reproduce these reactivity trends with a rapid red-to-colorless transition that is visible to the naked eye within 1 h of exposure and show a very low limit of detection (<5 ppm O2). Films are chemically and thermally robust and maintain up to >99% of their original colorimetric response when reused and subjected to multiple cycles of photooxygenation and O2 release. The simplicity and solution processability of these materials highlight their potential as "intelligent" inks for printable colorimetric sensors.

Studies of the regioselective ring-opening–closing mode of functionally different thiazolidine type enaminones: en route to the synthesis of trithiaazapentalene derivatives

Trithiaazapentalene derivatives were prepared by the reaction of 2-alkylidene-4-oxothiazolidines with Lawesson's reagent. They are classified as two structurally different trithiaazapentalene compounds that have different contributions of monocyclic 1,2-dithiole and 1,2,4-dithiazole structures and degrees of aromaticity of the bicyclic trithiaazapentalene system. The electron-donating ability of substituents at the C(5) position of the trithiaazapentalene system is recognized as the main cause for changes in π-electron distribution. This is the first complete study of substituent effects on the structure of trithiapentalenes.

Synthesis of nonsymmetrical dialkylamines on the basis of diphenylphosphinic amides

A facile method for the synthesis of nonsymmetrical dialkylamines (CnH2n+1)2NH (n = 1–12) using the Ph2P(O) protecting group was developed. The method includes successive transformation of monoalkylamines to primary diphenylphosphinic N-alkylamides Ph2P(O)NHR’ (R’ = CnH2n+1, n = 1–12) by the Todd—Atherton reaction, phase transfer N-alkylation of these compounds, and hydrolysis of the secondary amides Ph2P(O)NR’R″ thus formed. When the (EtO)2P(O) and Bu2P(O) protecting groups are used, N-alkylation of primary amides is accompanied by the formation of Et—O and P—N bond cleavage products, respectively. A study of the stability of the N-alkylamides R 2P(O)NHR’ (R = Ph, p-MeC6H4, p-CIC6H4, Bu) under strong alkaline conditions used in the phase transfer N-alkylation showed that an increase in the electron-donating ability of substituents at both the nitrogen atom and the phosphorus atom results in a decrease in the degree of P—N bond cleavage. The primary and secondary diphenylphosphinic amides containing a β-hydroxyethyl group at the nitrogen atom are extremely unstable under the alkaline conditions and are converted quantitatively to the diphenylphosphinic acid salt.

Theoretical studies on the electronic structures and spectroscopic properties for a series of Osmium(II)-2,2′,6′,2′′-terpyridine complexes

A series of Osmium(II) complexes [Os (trpy-R)2]2+(trpy=2,2′,6′,2′′-terpyridine and R=H (1), OH (2), and C6H5(3)) have been investigated by the density functional (DF) and ab initio calculations. The structures of 1–3 in the ground and excited states were fully optimized at the B3LYP and CIS level, respectively, and their absorption and emission spectra in the acetonitrile solution were obtained using the TD-DFT (B3LYP) method associated with the PCM model. The calculations indicated that, for 1–3, the variation of the substituents on the terpyridine ligand only slightly changes their geometrical structures in the ground and excited states but leads to a sizable difference in the electronic structures. The results show that the low-lying MLCT/ILCT transitions (at 446 (1), 465 (2), and 499 nm (3)) are red-shifted according to the electron-donating ability of substituents on the terpyridine ligand, but blue-shift trend of the high-lying ILCT transitions (at 301 (1), 297 (2), and 272 nm (3)). It also reveals that the lowest energy emissions of 1–3 at 649 nm, 656 nm, and 676 nm have the character of mixing 3[π*(trpy) → d(Os)] and 3 ππ* (3MLCT/3ILCT) transitions localized on the terpyridine ligand, which are identical to the transition properties of the lowest-energy absorptions.

ChemInform Abstract: Mechanistic Study on the Reaction of Phenyldiazomethanes with Singlet Oxygen: Formation and Cycloreversion of 1,2,3,4‐Dioxadiazole Intermediates.

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