Star polymer synthesis viaλ-orthogonal photochemistry.

We introduce a light induced sequence enabling λ-orthogonal star polymer formation via an arms-first approach, based on an α,ω-functional polymer carrying tetrazole and o-methyl benzaldehyde moieties, which upon irradiation can readily undergo cycloaddition with a trifunctional maleimide core. Depending on the wavelength, the telechelic strand can be attached to the core at either photo-reactive end.

Polymer-Fullerene Network Formation via Light-Induced Crosslinking.

A facile and efficient methodology for the formation of polymer-fullerene networks via a light-induced reaction is reported. The photochemical crosslinking is based on a nitrile imine-mediated tetrazole-ene cycloaddition reaction, which proceeds catalyst-free under UV-light irradiation (λmax = 320 nm) at ambient temperature. A tetrazole-functionalized polymer (Mn = 6500 g mol(-1) , Ð = 1.3) and fullerene C60 are employed for the formation of the hybrid networks. The tetrazole-functionalized polymer as well as the fullerene-containing networks are carefully characterized by NMR spectrometry, size exclusion chromatography, infrared spectroscopy, and elemental analysis. Furthermore, thermal analysis of the fullerene networks and their precursors is carried out. The current contribution thus induces an efficient platform technology for fullerene-based network formation.

A Light-Activated Reaction Manifold.

We introduce an efficient reaction manifold where the rate of a thermally induced ligation can be controlled by a photonic field via two competing reaction channels. The effectiveness of the reaction manifold is evidenced by following the transformations of macromolecular chain termini via high-resolution mass spectrometry and subsequently by selective block copolymer formation. The light-controlled reaction manifold consists of a so-called o-quinodimethane species, a photocaged diene, that reacts in the presence of light with suitable enes in a Diels-Alder reaction and undergoes a transformation into imines with amines in the absence of light. The chemical selectivity of the manifold is controlled by the amount of ene present in the reaction and can be adjusted from 100% imine formation (0% photo product) to 5% imine formation (95% photo product). The reported light-controlled reaction manifold is highly attractive because a simple external field is used to switch the selectivity of specific reaction channels.

Wavelength selective polymer network formation of end-functional star polymers.

A wavelength selective technique for light-induced network formation based on two photo-active moieties, namely ortho-methylbenzaldehyde and tetrazole is introduced. The network forming species are photo-reactive star polymers generated via reversible activation fragmentation chain transfer (RAFT) polymerization, allowing the network to be based on almost any vinylic monomer. Direct laser writing (DLW) allows to form any complex three-dimensional structure based on the photo-reactive star polymers.

λ-Orthogonal pericyclic macromolecular photoligation.

A photochemical strategy enabling λ-orthogonal reactions is introduced to construct macromolecular architectures and to encode variable functional groups with site-selective precision into a single molecule by the choice of wavelength. λ-Orthogonal pericyclic reactions proceed independently of one another by the selection of functional groups that absorb light of specific wavelengths. The power of the new concept is shown by a one-pot reaction of equimolar quantities of maleimide with two polymers carrying different maleimide-reactive endgroups, that is, a photoactive diene (photoenol) and a nitrile imine (tetrazole). Under selective irradiation at λ=310-350 nm, any maleimide (or activated ene) end-capped compound reacts exclusively with the photoenol functional polymer. After complete conversion of the photoenol, subsequent irradiation at λ=270-310 nm activates the reaction of the tetrazole group with functional enes. The versatility of the approach is shown by λ-orthogonal click reactions of complex maleimides, functional enes, and polymers to the central polymer scaffold.