The proof of concept for conditionally activatable photocages is demonstrated on a new vinyltetrazine-derivatized coumarin. The tetrazine form is disabled in terms of light-induced cargo release, however, bioorthogonal transformation of the modulating tetrazine moiety results in fully restored photoresponsivity. Irradiation of such a "click-armed" photocage with blue light leads to fast and efficient release of a set of caged model species, conjugated via various linkages. Live-cell applicability of the concept was also demonstrated by the conditional release of a fluorogenic probe using mitochondrial pretargeting.Ester-linked, crystalline, porous covalent organic frameworks (COFs) have been synthesized and structurally characterized. Transesterification reactions between ditopic 2-pyridinyl aromatic carboxylates and tri- or tetratopic phenols gave the corresponding ester-linked COFs. They crystallize as 2D structures in kgm (COF-119) and hcb (COF-120, 121, 122) topologies with surface areas of up to 2092 m2/g. Notably, crystalline COF-122 comprises edges spanning over 10 phenylene units, an aspect that had only been achieved in metal-organic frameworks. This work expands the scope of reticular chemistry to include, for the first time, crystalline ester-linked COFs related to common polyesters.The use of stereoelectronic interactions to control reactivity and selectivity has a long history in chemistry. The anomeric effect, one of the fundamental concepts in organic chemistry, describes the preferences of a substituent at the anomeric carbon in glycosides to adopt axial configuration when the anomeric group is an electronegative element such as oxygen or a halogen. The origin of the anomeric effect has been the subject of intense debate. Explanations capitalizing on either the delocalization of the endocyclic oxygen lone pair into the antibonding σ*(C-X) orbital or the minimization of the dipole-dipole interactions are currently the two leading theoretical models. Although the majority of experimental and theoretical studies have focused on the elements from groups 6 and 7, little is known about conformational preferences of tetrahydropyran rings substituted with a transition metal at the anomeric carbon and the role of these interactions in stereoselective synthesis. Here, we report studies on conformational and configurational preferences of organometallic complexes stabilized by vicinal heteroatoms. We provide computational evidence that late transition metals adopt the axial position in heterocycles or synclinal geometry in acyclic systems. Furthermore, the anomeric preferences of late transition metals correlate with the oxidation state of the metal and can be explained by hyperconjugative interactions between endocyclic heteroatom and the σ* acceptor orbitals of the C-M bond. In a broader context, this discovery provides insight into the role of previously unanticipated stereoelectronic effects that can be harnessed in the design of stereoselective reactions, including chemical glycosylation and enantioselective catalysis.The advent of the two-dimensional (2D) family of halide perovskites and their demonstration in 2D/three-dimensional (3D) hierarchical film structures broke new ground toward high device performance and good stability. The 2D Dion-Jacobson (DJ) phase halide perovskites are especially attractive in solar cells because of their superior charge transport properties. Here, we report on 2D DJ phase perovskites using a 3-(aminomethyl)piperidinium (3AMP) organic spacer for the fabrication of mixed Pb/Sn-based perovskites, exhibiting a narrow bandgap of 1.27 eV and a long carrier lifetime of 657.7 ns. Consequently, solar cells employing mixed 2D DJ 3AMP-based and 3D MA0.5FA0.5Pb0.5Sn0.5I3 (MA = methylammonium, FA = formamidinium) perovskite composites as light absorbers achieve enhanced efficiency and stability, giving a power conversion efficiency of 20.09% with a high open-circuit voltage of 0.88 V, a fill factor of 79.74%, and a short-circuit current density of 28.63 mA cm-2.  https://www.selleckchem.com/  The results provide an effective strategy to improve the performance of single-junction narrow-bandgap solar cells and, potentially, to give a highly efficient alternative to bottom solar cells in tandem devices.The combined use of reaction kinetic analysis, ultrafast spectroscopy, and stoichiometric organometallic studies has enabled the elucidation of the mechanistic underpinnings to a photocatalytic C-N cross-coupling reaction. Steady-state and ultrafast spectroscopic techniques were used to track the excited-state evolution of the employed iridium photocatalyst, determine the resting states of both iridium and nickel catalysts, and uncover the photochemical mechanism for reductive activation of the nickel cocatalyst. Stoichiometric organometallic studies along with a comprehensive kinetic study of the reaction, including rate-driving force analysis, unveiled the crucial role of photocatalysis in both initiating and sustaining a Ni(I)/Ni(III) cross-coupling mechanism. The insights gleaned from this study further enabled the discovery of a new photocatalyst providing a >30-fold rate increase.Time Dependent Density Functional Theory has been used to assist the design and synthesis of a series thioxanthone triplet sensitizers. Calculated energies of the triplet excited state (ET) informed both the type and position of auxochromes placed on the thioxanthone core, enabling fine-tuning of the UV-vis absorptions and associated triplet energies. The calculated results were highly consistent with experimental observation in both the order of the λmax and ET values. The synthesized compounds were then evaluated for their efficacies as triplet sensitizers in a variety of UV and visible light preparative photochemical reactions. The results of this study exceeded expectations; in particular [2 + 2] cycloaddition chemistry that had previously been sensitized in the UV was found to undergo cycloaddition at 455 nm (blue) with a 2- to 9-fold increase in productivity (g/h) relative to input power. This study demonstrates the ability of powerful modern computational methods to aid in the design of successful and productive triplet sensitized photochemical reactions.