Electronic and steric substituent effects on the fluorescence emission of 2-pyrazoline derivatives.

A series of substituted 2-pyrazolines were synthesized, and the steric and electronic effects of substituents on the C3 - and C5 -positions of the heterocyclic ring on their fluorescent ability were investigated. Two different conjugative intramolecular charge transfer (ICT) and intramolecular charge transfer through space (spiro-conjugation) affect the fluorescence intensity of these compounds. The extent of the ICT process and spiro-conjugation depends on the electronic nature of the additional substitution and its position on the attached aryl rings. In addition, the effects of the concentration and the solvent polarity on the fluorescence emission were studied. Density functional theory (DFT) calculations were carried out to gain insight into the geometric, electronic, and spectroscopic properties of the pyrazoline derivatives. The results of both experimental and computational studies explain the effects of the geometrical orientation of the C3 - and C5 -aryl rings toward the heterocyclic ring and also the electronic nature of their additional substitutions on the fluorescence intensity.

Post-synthetic modifications of covalent organic frameworks (COFs) for diverse applications.

Covalent organic frameworks (COFs) are porous and crystalline organic polymers, which have found usage in various fields. These frameworks are tailorable through the introduction of diverse functionalities into the platform. Indeed, functionality plays a key role in their different applications. However, sometimes functional groups are not compatible with reaction conditions or can compete and interfere with other groups of monomers in the direct synthetic method. Also, pre-synthesis of bulky moieties in COFs can negatively affect crystal formation. To avoid these problems a post-synthetic modification (PSM) approach is a helpful tactic. Also, with the assistance of this strategy porous size can be tunable and stability can be improved without considerable effect on the crystallite. In addition, conductivity, hydrophobicity/ hydrophilicity, and chirality are among the features that can be reformed with this method. In this review, different types of PSM strategies based on recent articles have been divided into four categories: (i) post-functionalization, (ii) post-metalation, (iii) chemical locking, and (iv) host-guest post-modifications. Post-functionalization and chemical locking methods are based on covalent bond formation while in post-metalation and host-guest post-modifications, non-covalent bonds are formed. Also, the potential of these post-modified COFs in energy storage and conversion (lithium-sulfur batteries, hydrogen storage, proton-exchange membrane fuel cells, and water splitting), heterogeneous catalysts, food safety evaluation, gas separation, environmental domains (greenhouse gas capture, radioactive element uptake, and water remediation), and biological applications (drug delivery, biosensors, biomarker capture, chiral column chromatography, and solid-state smart nanochannels) have been discussed.