Structure-Photochemical Function Relationships in Nitrogen-Containing Heterocyclic Aromatic Photobases Derived from Quinoline

<p>Photobases are compounds which become strong bases after electronic excitaton into a charge-transfer excited state. Recent experimental studies have highlighted the photobasicity of the 5-R quinoline compounds, demonstrating a strong substituent dependence to the pK_a^*. Here we describe our systematic study of how the photobasicity of four families of nitrogen-containing heterocyclic aromatics are tuned through substituents. We show that substituent position and identity both significantly impact the pK_a^*. We demonstrate that the substituent effects are additive and identify many disubstituted compounds with substantially greater photobasicity than the most photobasic 5-R quinoline compound identified previously. We show that the addition of a second fused benzene ring to quinoline, along with two electron-donating substituents, lowers the vertical excitation energy into the visible while still maintaining a pK_a^* > 14. Overall, the structure-function relationships developed in this study provide new insights to guide the development of new photocatalysts that employ photobasicity. </p>

Structure-Photochemical Function Relationships in Nitrogen-Containing Heterocyclic Aromatic Photobases Derived from Quinoline

<p>Photobases are compounds which become strong bases after electronic excitaton into a charge-transfer excited state. Recent experimental studies have highlighted the photobasicity of the 5-R quinoline compounds, demonstrating a strong substituent dependence to the pK_a^*. Here we describe our systematic study of how the photobasicity of four families of nitrogen-containing heterocyclic aromatics are tuned through substituents. We show that substituent position and identity both significantly impact the pK_a^*. We demonstrate that the substituent effects are additive and identify many disubstituted compounds with substantially greater photobasicity than the most photobasic 5-R quinoline compound identified previously. We show that the addition of a second fused benzene ring to quinoline, along with two electron-donating substituents, lowers the vertical excitation energy into the visible while still maintaining a pK_a^* > 14. Overall, the structure-function relationships developed in this study provide new insights to guide the development of new photocatalysts that employ photobasicity. </p>

Atom economical coupling of benzophenone and N-heterocyclic aromatics with SmI2

The mechanism of the direct coupling of benzophenone with N-heteroaromatics leading to pyridinemethanols using SmI2 as a unique reagent is unraveled.

Structure-Photochemical Function Relationships in Nitrogen-Containing Heterocyclic Aromatic Photobases Derived from Quinoline

<p>Photobases are compounds which become strong bases after electronic excitaton into a charge-transfer excited state. Recent experimental studies have highlighted the photobasicity of the 5-R quinoline compounds, demonstrating a strong substituent dependence to the pK_a^*. Here we describe our systematic study of how the photobasicity of four families of nitrogen-containing heterocyclic aromatics are tuned through substituents. We show that substituent position and identity both significantly impact the pK_a^*. We demonstrate that the substituent effects are additive and identify many disubstituted compounds with substantially greater photobasicity than the most photobasic 5-R quinoline compound identified previously. We show that the addition of a second fused benzene ring to quinoline, along with two electron-donating substituents, lowers the vertical excitation energy into the visible while still maintaining a pK_a^* > 14. Overall, the structure-function relationships developed in this study provide new insights to guide the development of new photocatalysts that employ photobasicity. </p>

Chemical characterization of laboratory-generated tar ball particles

The chemical properties of laboratory-generated tar ball (Lab-TB) particles produced from dry distillate (wood tars) of three different wood species in the laboratory were investigated by analytical techniques that had never been used before for their characterization. The elemental compositions of laboratory-generated tar balls (Lab-TBs) from three tree species were very similar to one another and to those characteristic of atmospheric tar balls (TBs) collected from the savanna fire during the SAFARI 2000 sampling campaign. The O ∕ C and H ∕ C molar ratios of the generated Lab-TBs were at the upper limit characteristic of soot particles. The Fourier transform infrared spectroscopy (FT-IR) spectra of the generated Lab-TBs were very similar to one another as well and also showed some similarity with those of atmospheric humic-like substances (HULIS). The FT-IR measurements indicated that Lab-TBs have a higher proportion of aromatic structure than HULIS and the oxygen atoms of Lab-TBs are mainly found in hydroxyl and keto functional groups. Whereas Raman activity was detected in the starting materials of the Lab-TBs (wood tars) in the range of 1000–1800 cm−1, the Raman spectra of TBs were dominated by two pronounced bands with intensity maxima near 1580 (G band) and 1350 cm−1 (D band), indicating the presence of sp2-hybridized carbon structures and disorder in them, respectively. In the Py-GC-MS chromatograms of the Lab-TBs mostly aromatic compounds (aromatic hydrocarbons, oxygenated aromatics and heterocyclic aromatics) were identified in accordance with the results of Raman and FT-IR spectroscopy. According to organic carbon ∕ elemental carbon (OC ∕ EC) analysis using EUSAAR_2 thermal protocol, 22 % of the total carbon content of Lab-TBs was identified as EC, contrary to expectations based on the current understanding that negligible if any EC is present in this sub-fraction of the brown carbon family. Our results suggest that spherical atmospheric TBs with high C ∕ O molar ratios are closer to BC in many of their properties than to weakly absorbing HULIS.

Chemical characterization of laboratory-generated tar ball particles

The chemical properties of tar ball (TB) particles generated from dry distillate (wood tars) of three different wood species in the laboratory were investigated by analytical techniques that had never been used before, for their characterization. The elemental composition of TB particles from three tree species were very similar to one another and to those characteristic for atmospheric tar balls (TBs) collected from savanna fire during the SAFARI 2000 sampling campaign. The O / C and H / C molar ratios of the generated TBs were at the upper limit characteristic for soot particles. The FT-IR spectra of the generated TBs were very similar to one another as well and also showed some similarity with those of atmospheric humic-like substances (HULIS). The FT-IR measurements indicated that laboratory-generated TBs have a higher proportion of aromatic structure than HULIS and the oxygen atoms of TBs are mainly found in hydroxyl and keto functional groups. Whereas the starting materials of the TBs (wood tars) were Raman inactive in the range of 1000–1800 cm−1, the Raman spectra of TBs were dominated by two pronounced bands with intensity maxima near 1580 (G band) and 1350 cm−1 (D band), indicating the presence of sp2-hybridised carbon structures and disorder in them, respectively. In the Py-GC-MS chromatograms of the laboratory-generated TBs mostly aromatic compounds (aromatic hydrocarbons, oxygenated aromatics and heterocyclic aromatics) were identified in accordance with the results of Raman and FT-IR spectroscopy. According to OC / EC analysis using EUSAAR_2 long thermal protocol, 22 % of the total carbon content of laboratory-generated TBs was identified as elemental carbon (EC), contrary to expectations based on the current understanding that negligible if any EC is present in this sub-fraction of the brown carbon family. Our results suggest that spherical atmospheric TBs with high C / O molar ratios are closer to BC in many of their properties than to weakly absorbing HULIS.