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.

Wavelength-Dependent Activation of Photoacids and Bases.

Photoacids and bases allow remote control over pH in reaction solutions, which is of fundamental importance to an array of applications. Herein, we determine the wavelength-by-wavelength resolved photoreactivity of triarylsulfonium hexafluorophosphate salts as a representative photoacid generator and p-(benzoyl)benzyl triethylammonium tetraphenylborate as a photobase generator, constructing a wavelength-resolved photochemical action plot for each of the compounds. We monitor the pH change of the solution on-line within the cavity of the laser vial and demonstrate a marked mismatch between the absorption spectrum of the photoacid and base with the photochemical action plot, unveiling reactivity at very low absorptivities. Our findings are of critical importance for the use of photoacids and bases, unambiguously demonstrating that absorption is no guide to chemical reactivity with critical consequences for the wavelength employed in applications of photoacids and bases.

Cyclodextrin 'Chaperones' Enable Quasi-Ideal Supramolecular Network Formation and Enhanced Photodimerization of Hydrophobic, Red-shifted Photoswitches in Water.

Precision-engineered light-triggered hydrogels are important for a diversity of applications. However, fields such as biomaterials require wavelength outside the harsh UV regime to prevent photodamage, typically requiring chromophores with extended π-conjugation that suffer from poor water solubility. Herein, we demonstrate how cyclodextrins can be used as auxiliary agents to not only solubilize such chromophores, but even to preorganize them in a 2 : 2 host-guest inclusion complex to facilitate photodimerization. We apply our concept to styrylpyrene-end-functionalized star-shaped polyethylene glycols (sPEGs). We initially unravel details of the host-guest inclusion complex using spectroscopy and mass spectrometry to give clear evidence of a 2 : 2 complex formation. Subsequently, we show that the resultant supramolecularly linked hydrogels conform to theories of supramolecular quasi-ideal model networks, and derive details on their association dynamics using in-depth rheological measurements and kinetic models. By comparing sPEGs of different arm length, we further elucidate the model network topology and the accessible mechanical property space. The photo-mediated dimerization proceeds smoothly, allowing to transform the supramolecular model networks into covalent ones. We submit that our strategy opens avenues for executing hydrophobic photochemistry in aqueous environments with enhanced control over reactivity, hydrogel topology or programmable mechanical properties.

Photo- and halochromism of spiropyran-based main-chain polymers.

Advanced functional polymeric materials based on spiropyrans (SPs) feature multi-stimuli responsive characteristics, such as a change in color with exposure to light (photochromism) or acids (halochromism). The inclusion of stimuli-responsive molecules in general - and SPs in particular - as main-chain repeating units is a scarcely explored macromolecular architecture compared to side chain responsive polymers. Herein, we establish the effects of substitution patterns on SPs within a homopolymer main-chain synthesized via head-to-tail Acyclic Diene METathesis (ADMET) polymerization. We unambiguously demonstrate that varying the location of the ester group (-OCOR) on the chromophore, which is essential to incorporate the SPs in the polymer backbone, determines the photo- and halochromism of the resulting polymers. While one polymer shows effective photochromism and resistance towards acids, the opposite - weak photochromism and effective response to acid - is observed for an isomeric polymer, simply by changing the position of the ester-linker relative to the benzopyran oxygen on the chromene unit. Our strategy represents a simple approach to manipulate the stimuli-response of main-chain SP bearing polymers and highlights the critical importance of isomeric molecular constitution on main-chain stimuli-sensitive polymers as emerging materials.

The Macromolecular Design of Poly(styrene-isoprene-styrene) (SIS) Copolymers Defines their Performance in Flexible Electrothermal Composite Heaters.

Electric cars are desirable for their environmental and economic benefits yet face limitations in range in cold weather due to the increased energy demands for cabin heating. To provide efficient heating for vehicles, flexible composite electrothermal heaters offer a viable solution owing to their lightweight design, efficiency, and adaptability for use within and beyond vehicle interiors. The current study aims to improve electrothermal heater stability and performance by understanding the impact of the polymer structure on composite properties. We explore how the presence and molecular structure of olefinic bonds within the polyisoprene block of styrenic triblock copolymers affect thermal stability and performance. Composite electrothermal heaters were fabricated by dispersing carbon black (CB) as the heating material in three triblock copolymer matrices, poly(styrene-1,4-isoprene-styrene) (1,4-SIS), poly(styrene-3,4-isoprene-styrene) (3,4-SIS), and its hydrogenated version poly(styrene-ethylene-propylene-styrene) (SEPS). The chemical structure and thermal properties of each copolymer were linked to electrothermal performance measurements of composite heaters to establish structure-function relationships. Notably, 3,4-SIS with 28 wt % CB demonstrated the highest thermal and electrical conductivity, resulting in uniform heat distribution. The outcomes unambiguously demonstrate that the olefinic structure of SIS copolymers enhances the electric and thermal conductivity, leading to enhanced electrothermal performance of prototype heaters compared to that of the hydrogenated copolymer.

Förster resonance energy transfer within single chain nanoparticles.

Single chain nanoparticles (SCNPs) are a highly versatile polymer architecture consisting of single polymer chains that are intramolecularly crosslinked. Currently, SCNPs are discussed as powerful macromolecular architectures for catalysis, delivery and sensors. Herein, we introduce a methodology based on Förster Resonance Energy Transfer (FRET) to evidence the folding of single polymer chains into SCNPs via fluorescence readout. We initially introduce a molecular FRET pair based on a bimane and nitrobenzoxadiazole (NBD) moiety and study its fluorescence properties in different solvents. We subsequently construct a low dispersity polymer chain carrying NBD units, while exploiting the bimane units for intramolecular chain collapse. Upon chain collapse and SCNP formation - thus bringing bimane and NBD units into close proximity - the SCNPs report their folded state by a strong and unambiguous FRET fluorescence signal. The herein introduced reporting of the folding state of SCNPs solely relies on an optical readout, opening avenues to monitoring SCNP folding without recourse to complex analytical methodologies.

Access to Main-Chain Photoswitching Polymers via Hydroxyl-yne Click Polymerization.

Main-chain stimuli-responsive polymers synthesized via polymerization techniques that do not rely on metal-based catalysis are highly desirable for economic reasons and to avoid metal-polymer interactions. Herein, we introduce a metal-free head-to-tail organobase-catalyzed hydroxyl-yne click polymerization of an AB-type monomer to realize photoswitchable polymers featuring α-bismines as main-chain repeating units. The prepared main-chain α-bisimine-based polymers show excellent photoswitching in solution. We further post-functionalize the obtained polymers with various thiol compounds via thiol-Michael reactions to significantly lower the glass transition temperature (Tg), likely to be beneficial for the photoswitching process in the solid state. Thus, the herein introduced polymerization technique not only provides metal-free access to main-chain stimuli-responsive polymers, but also allows for the flexible post-modification of the obtained polymers to generate advanced macromolecular architectures with tunable properties.

Photo-induced synthesis of polymeric nanoparticles and chemiluminescent degradable materials via flow chemistry.

We report the photo-induced, additive-free, continuous synthesis of polymeric particles using flow chemistry. Not only can these particles be formed under ambient conditions in a solely light-induced precipitation polymerisation, they can be prepared via continuous flow techniques to up-scale the synthetic process. We carefully assess the flow chemical parameters and analyse the resulting particles quantitatively using scanning electron microscopy (SEM). Particle formation is a direct result of the step-growth polymerisation via a photochemically induced AA + BB Diels-Alder reaction, which we herein base on the dialdehyde monomer (AA) derived from the sustainable precursor, thymol. By employing a peroxyoxalate bismaleimide (BB), we introduce particles that can be selectively degraded on-demand, self-reported by light emission through chemiluminescence.

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.

Two- and three-photon processes during photopolymerization in 3D laser printing.

The performance of a photoinitiator is key to control efficiency and resolution in 3D laser nanoprinting. Upon light absorption, a cascade of competing photophysical processes leads to photochemical reactions toward radical formation that initiates free radical polymerization (FRP). Here, we investigate 7-diethylamino-3-thenoylcoumarin (DETC), belonging to an efficient and frequently used class of photoinitiators in 3D laser printing, and explain the molecular bases of FRP initiation upon DETC photoactivation. Depending on the presence of a co-initiator, DETC causes radical generation either upon two-photon- or three-photon excitation, but the mechanism for these processes is not well understood so far. Here, we show that the unique three-photon based radical formation by DETC, in the absence of a co-initiator, results from its excitation to highly excited triplet states. They allow a hydrogen-atom transfer reaction from the pentaerythritol triacrylate (PETA) monomer to DETC, enabling the formation of the reactive PETA alkyl radical, which initiates FRP. The formation of active DETC radicals is demonstrated to be less spontaneous. In contrast, photoinitiation in the presence of an onium salt co-initiator proceeds via intermolecular electron transfer after the photosensitization of the photoinitiator to the lowest triplet excited state. Our quantum mechanical calculations demonstrate photophysical processes upon the multiphoton activation of DETC and explain different reactions for the radical formation upon DETC photoactivation. This investigation for the first time describes possible pathways of FRP initiation in 3D laser nanoprinting and permits further rational design of efficient photoinitiators to increase the speed and sensitivity of 3D laser nanoprinting.

Visible light-induced switching of soft matter materials properties based on thioindigo photoswitches.

Thioindigos are visible light responsive photoswitches with excellent spatial control over the conformational change between their trans- and cis- isomers. However, they possess limited solubility in all conventional organic solvents and polymers, hindering their application in soft matter materials. Herein, we introduce a strategy for the covalent insertion of thioindigo units into polymer main chains, enabling thioindigos to function within crosslinked polymeric hydrogels. We overcome their solubility issue by developing a thioindigo bismethacrylate linker able to undergo radical initiated thiol-ene reaction for step-growth polymerization, generating indigo-containing polymers. The optimal wavelength for the reversible trans-/cis- isomerisation of thioindigo was elucidated by constructing a detailed photochemical action plot of their switching efficiencies at a wide range of monochromatic wavelengths. Critically, indigo-containing polymers display significant photoswitching of the materials' optical and physical properties in organic solvents and water. Furthermore, the photoswitching of thioindigo within crosslinked structures enables visible light induced modulation of the hydrogel stiffness. Both the thioindigo-containing hydrogels and photoswitching processes are non-toxic to cells, thus offering opportunities for advanced applications in soft matter materials and biology-related research.