Experimental and Theoretical Study on the Homodimerization Mechanism of 3-Acetylcoumarin.

In the present study, the reaction conditions for homodimerization process of 3-acetylcoumarin were achieved under sonication using combination of zinc and metallic salt (ZnCl2 or Zn(OAc)2). Appropriate frequency and sound amplitude have been identified as significant variables for the initiation of the reaction. On the base of first principal calculations and experimental results, the mechanism of the reaction was investigated. The relative stability of the possible intermediates has been compared, including evaluation on the ionic and radical reaction pathways for the dimerization process. Theoretical results suggested that the radical mechanism is more favorable. The C-C bond formation between the calculated radical intermediates occurs spontaneously (∆G = -214 kJ/mol for ZnCl2, -163 kJ/mol in the case of Zn(OAc)2), which proves the possibility for the homodimerization of 3-acetylcoumarin via formation of radical species. Both experimental and theoretical data clarified the activation role of the solvent on the reactivity of the Zn-salt. The formation of complexes of solvent molecules with Zn-atom from the ZnCl2 reduces the energy barrier for the dissociation of Zn-Cl bond and facilitate the formation of the dimeric product.

Efficient Synthesis of Fluorescent Coumarins and Phosphorous-Containing Coumarin-Type Heterocycles via Palladium Catalyzed Cross-Coupling Reactions.

Quantum-chemical calculations on the spectral properties of some aryl substituted 3-phosphonocoumarins were performed, and the effect of the substituents in the aryl moiety was evaluated. The structures possessing promising fluorescent properties were successfully synthesized via Suzuki and Sonogashira cross-coupling. The synthetic protocol was also applied for the phosphorous chemoisomer of 3-phosphonocoumarin, 1,2-benzoxaphosphorin, and their carboxylate analogues. The optical properties of the arylated and alkynylated products were experimentally determined. The obtained quantum-chemical and experimental results give the possibility for a fine tuning of the optical properties of phosphorous-containing coumarin systems by altering the substituent at its C-6 position.

Direct Construction of Isomeric Benzobisoxazole-Vinylene-Linked Covalent Organic Frameworks with Distinct Photocatalytic Properties.

Vinylene/olefin-linked two-dimensional covalent organic frameworks (v-2D-COFs) have emerged as advanced semiconducting materials with excellent in-plane conjugation, high chemical stabilities, and precisely tunable electronic structures. Exploring new linkage chemistry for the reticular construction of v-2D-COFs remains in infancy and challenging. Herein, we present a solid-state benzobisoxazole-mediated aldol polycondensation reaction for the construction of two novel isomeric benzobisoxazole-bridged v-2D-COFs (v-2D-COF-NO1 and v-2D-COF-NO2) with trans and cis configurations of benzobisoxazole. Interestingly, the isomeric benzobisoxazole linkers endow the two v-2D-COFs with distinct optoelectronic and electrochemical properties, ranging from light absorption and emission to charge-transfer properties. When employed as the photocathode, v-2D-COF-NO1 exhibits a photocurrent of up to ∼18 µA/cm2 under AM 1.5G irradiation at -0.3 V vs reversible hydrogen electrode (RHE), which is twice the value of v-2D-COF-NO2 (∼9.1 µA/cm2). With Pt as a cocatalyst, v-2D-COF-NO1 demonstrates a photocatalytic hydrogen evolution rate of ∼1.97 mmol h-1 g-1, also in clear contrast to that of v-2D-COF-NO2 (∼0.86 mmol h-1 g-1) under identical conditions. This work demonstrates the synthesis of v-2D-COFs via benzobisoxazole-mediated aldol polycondensation with isomeric structures and distinct photocatalytic properties.

Defect Formation, T-Atom Substitution and Adsorption of Guest Molecules in MSE-Type Zeolite Framework-DFT Modeling.

We used computational modeling, based on Density Functional Theory, to help understand the preference for the formation of silanol nests and the substitution of Si by Ti or Al in different crystallographic positions of the MSE-type framework. All these processes were found to be energetically favorable by more than 100 kJ/mol. We suggested an approach for experimental identification of the T atom position in Ti-MCM-68 zeolite via simulation of infrared spectra of pyridine and acetonitrile adsorption at Ti. The modeling of adsorption of hydrogen peroxide at Ti center in the framework has shown that the molecular adsorption was preferred over the dissociative adsorption by 20 to 40 kJ/mol in the presence or absence of neighboring T-atom vacancy, respectively.