Photochemical Action Plots Reveal Red-shifted Wavelength-dependent Photoproduct Distributions.

Photochemical action plots are a powerful tool for mapping photochemical reaction outcomes wavelength-by-wavelength. Typically, they map either the depletion of a reactant or the formation of a specific product as a function of wavelength. Herein, we exploit action plots to simultaneously map the formation of several photochemical products from a single chromophore. We demonstrate that the wavelength-resolved mapping of two reaction products formed during the irradiation of a chalcone species not only shows wavelength dependence - exhibiting the typical strong red-shift of the photochemical reactivity compared to the absorbance spectrum of the chromophore - but also a strong wavelength selectivity with remarkably different product distributions resulting from different irradiation wavelengths.

Photochemical Action Plots Map Orthogonal Reactivity in Photochemical Release Systems.

The wavelength-by-wavelength resolved photoreactivity of two photo-caged carboxylic acids, i. e. 7-(diethylamino)-coumarin- and 3-perylene-modified substrates, is investigated via photochemical action plots. The observed wavelength-dependent reactivity of the chromophores is contrasted with their absorption profile. The photochemical action plots reveal a remarkable mismatch between the maximum reactivity and the absorbance. Through the action plot data, the study is able to uncover photochemical reactivity maxima at longer and shorter wavelengths, where the molar absorptivity of the chromophores is strongly reduced. Finally, the laser experiments are translated to light emitting diode (LED) irradiation and show efficient visible-light-induced release in a near fully wavelength-orthogonal, sequence-independent fashion (λLED1 = 405 nm, λLED2 = 505 nm) with both chromophores in the same reaction solution. The herein pioneered wavelength orthogonal release systems open an avenue for releasing two different molecular cargos with visible light in a fully orthogonal fashion.

How molecular architecture defines quantum yields.

Understanding the intricate relationship between molecular architecture and function underpins most challenges at the forefront of chemical innovation. Bond-forming reactions are particularly influenced by the topology of a chemical structure, both on small molecule scale and in larger macromolecular frameworks. Herein, we elucidate the impact that molecular architecture has on the photo-induced cyclisations of a series of monodisperse macromolecules with defined spacers between photodimerisable moieties, and examine the relationship between propensity for intramolecular cyclisation and intermolecular network formation. We demonstrate a goldilocks zone of maximum reactivity between the sterically hindered and entropically limited regimes with a quantum yield of intramolecular cyclisation that is nearly an order of magnitude higher than the lowest value. As a result of the molecular design of trifunctional macromolecules, their quantum yields can be deconvoluted into the formation of two different cyclic isomers, as rationalised with molecular dynamics simulations. Critically, we visualise our solution-based studies with light-based additive manufacturing. We formulate four photoresists for microprinting, revealing that the precise positioning of functional groups is critical for resist performance, with lower intramolecular quantum yields leading to higher-quality printing in most cases.

Aqueous electrochemically-triggered atom transfer radical polymerization.

Simplified electrochemical atom transfer radical polymerization (seATRP) using CuII-N-propyl pyridineimine complexes (CuII(NPPI)2) is reported for the first time. In aqueous solution, using oligo(ethylene glycol) methyl ether methacrylate (OEGMA), standard electrolysis conditions yield POEGMA with good control over molecular weight distribution (D m < 1.35). Interestingly, the polymerizations are not under complete electrochemical control, as monomer conversion continues when electrolysis is halted. Alternatively, it is shown that the extent and rate of polymerization depends upon an initial period of electrolysis. Thus, it is proposed that seATRP using CuII(NPPI)2 follows an electrochemically-triggered, rather than electrochemically mediated, ATRP mechanism, which distinguishes them from other CuIIL complexes that have been previously reported in the literature.