A revised bonding model for diarylhalonium salts, that involves partial s-orbital contribution, provides new insight into periodic trends in structure and reactivity.

This work demonstrates the impact of intramolecular hydrogen bonding (H-bonding) on the calculated pKa of octahedral tris-(pyridinethiolato)nickel (II), [Ni(PyS)3]-, proton reduction catalysts. Density Functional Theory (DFT) calculations on a [Ni(PyS)3]-...

Arynes are highly reactive intermediates that may be used strategically in synthesis by trapping with arynophilic reagents. However, “arynophilicity” of such reagents is almost completely anecdotal and predicting which ones will be efficient traps is often challenging. Here, we describe a systematic study to parameterize the arynophilicity of a wide range of reagents known to trap arynes. A relative reactivity scale, based on one-pot competition experiments, is presented by using furan as a reference arynophile and 3-chlorobenzyne as a the aryne. Greater than 15 arynophiles that react in pericyclic reactions, nucleophilic addition, and σ-bond insertion reactions are parameterized with arynophilicity (A) values, and multiple aryne precursors are applicable.

The methoxy‐ and fluoro‐derivatives of meta‐nitrophenylacetic acid (mNPA) chromophores undergo photodecarboxylation with comparable quantum yields (Φ) to unsubstituted mNPA, but uncage at red‐shifted excitation wavelengths. This observation prompted us to investigate DPAdeCageOMe (2‐[bis(pyridin‐2‐ylmethyl)amino]‐2‐(4‐methoxy‐3‐nitrophenyl)acetic acid) and DPAdeCageF (2‐[bis(pyridin‐2‐ylmethyl)amino]‐2‐(4‐fluoro‐3‐nitrophenyl)acetic acid) as Zn2+ photocages. DPAdeCageOMe has a high Φ and exhibits other photophysical properties comparable to XDPAdeCage ({bis[(2‐pyridyl)methyl]amino}(9‐oxo‐2‐xanthenyl) acetic acid), the best preforming Zn2+ photocage reported to date. Since the synthesis of DPAdeCageOMe is more straightforward than XDPACage, the new photocage will be a highly competitive tool for biological applications.

Ionic resorcinarenes successfully disrupt the aggregation of αA66-80 crystallin peptide related to cataracts. The results show functionalized resorcinarenes as potential agents to reverse the aggregation of α-crystallin dominant in eye cataracts.