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The development of light‐responsive molecular tools enables spatiotemporal control of biochemical processes with superior precision. Amongst these molecular tools, photolabile caging groups are employed to prevent critical binding interactions between a bioactive molecule and its corresponding target. Only upon irradiation with light, the bioactive is released in its 'active' form and is now readily available to bind to its target. Coumarin‐derived caging groups constitute one of the most popular classes of photolabile protecting groups, due to their facile synthetic accessibility, ease of tuning photophysical properties via structural modification and rapid photolysis reactions. Herein, we highlight the recent progress made on the development of coumarin‐derived caging groups, in which the red‐shifting of absorption spectra, improving aqueous solubility and tailoring sub‐cellular localisation has been of particular interest. [ABSTRACT FROM AUTHOR]

Co(III) complexes of the N-heterocyclic carbene ligand PY4Im (PY4Im = (1,3-bis(bis(2-pyridyl)methyl)imidazol-2-ylidene)) having the general formula [(PY4Im)Co(X)](ClO4)n (X = NCMe; n = 3: OH−, N3−, NCS−, ONO−, F−; n = 2: O2CO2−, n = 1; (N3−)3, n = 0) were prepared and structurally characterised. X-ray structural data are consistent with the presence of a trans influence due to the coordinated carbene carbon, and this is also supported by computational results. 13C NMR spectra of the complexes did not display peaks corresponding to the carbene carbon, except in the case of the [(PY4Im)Co(O2CO)]+ cation, where a peak at δ = 170.21 ppm was observed. However, HMBC spectra allowed indirect determination of the chemical shifts of the carbene carbon in the remaining complexes, owing to the geometry of the PY4Im ligand. Calculated 13C chemical shifts for the complexes showed very good agreement with the experimental values for all but the carbene carbon atoms in all cases. [ABSTRACT FROM AUTHOR]

The development of new and effective therapeutics is reliant on the ability to study the underlying mechanisms of potential drug targets in live cells and multicellular systems. A persistent challenge in many drug development programmes is poor selectivity, which can obscure the mechanisms involved and lead to poorly understood modes of action. In efforts to improve our understanding of these complex processes, small molecule inhibitors have been developed in which their OFF/ON therapeutic activity can be toggled using light. Photopharmacology is devoted to using light to modulate drugs. Herein, we highlight the recent progress made towards the development of light‐responsive small molecule inhibitors of selected enzymatic targets. Given the size of this field, literature from 2015 onwards has been reviewed. [ABSTRACT FROM AUTHOR]

An improved synthesis and structuralreassignment of the classIIa selective histone deacetylase (HDAC) inhibitor MC1568 are described. [ABSTRACT FROM AUTHOR]

The syntheses of the tripodal tetraamine ligands 2‐(pyridin‐2‐yl)‐N,N‐bis(quinolin‐2‐ylmethyl)ethan‐1‐amine (DQPEA), N‐(pyridin‐2‐ylmethyl)‐2‐(quinolin‐2‐yl)‐N‐(2‐(quinolin‐2‐yl)ethyl)ethan‐1‐amine (DQEPMA), 2‐(pyridin‐2‐yl)‐N,N‐bis(2‐(quinolin‐2‐yl)ethyl)ethan‐1‐amine (DQEPEA), N,N‐bis(pyridin‐2‐ylmethyl)‐2‐(quinolin‐2‐yl)ethan‐1‐amine (QEDPMA), and 2‐(pyridin‐2‐yl)‐N‐(2‐(pyridin‐2‐yl)ethyl)‐N‐(2‐(quinolin‐2‐yl)ethyl)ethan‐1‐amine (QEDPEA) containing mixed quinolyl and pyridyl moieties are reported, with 2‐vinylquinoline being used to attach quinolylethyl arms to the aliphatic N atom. X‐ray crystal structures of [(Mn(DQPEA))2O2](ClO4)2 ⋅ (CH3CN)2, [Cu(DQPEA)NCCH3](ClO4)2, [Zn(DQPEA)NCCH3](ClO4)2, [Pd(DQEPEA)Cl]Cl ⋅ 11H2O are detailed, with four, five, and six‐coordination observed. In addition, the dimeric complex [(DPEA)Co(μ‐OH)3Co(DPEA)](ClO4)3 ⋅ 0.5H2O ⋅ MeCN containing the tridentate DPEA ligand formed by N‐dealkylation of QEDPEA is reported. Calculations suggest that the very short Co…Co distance of 2.5946(6) Å in this complex is unlikely to be due to a Co−Co bond. [ABSTRACT FROM AUTHOR]

The species originally reported as [Co(bipy) 2 O 2 BOH]·[B 5 O 6 (OH) 4 ]·H 3 BO 3 ·H 3 O·H 2 O, a Co(II) complex containing a chelated O 2 BOH 2- ligand, is shown to be [Co(bipy) 2 O 2 CO]·[B 5 O 6 (OH) 4 ]·H 3 BO 3 ·2H 2 O, a Co(III) complex containing a chelated O 2 CO 2- ligand. This was confirmed by 1 H and 13 C NMR, MS, IR, and an X-ray crystal structure.

The development of new and effective therapeutics is reliant on the ability to study the underlying mechanisms of potential drug targets in live cells and multicellular systems. A persistent challenge in many drug development programmes is poor selectivity, which can obscure the mechanisms involved and lead to poorly understood modes of action. In efforts to improve our understanding of these complex processes, small molecule inhibitors have been developed in which their OFF/ON therapeutic activity can be toggled using light. Photopharmacology is devoted to using light to modulate drugs. Herein, we highlight the recent progress made towards the development of light-responsive small molecule inhibitors of selected enzymatic targets. Given the size of this field, literature from 2015 onwards has been reviewed., (© 2022 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)