Hexaarylbiimidazoles Research Articles

Cyclic Perfluoropolyether: Distinct Film Formability and Thermostabilization Upon Recyclable Cyclic-Linear Topological Transformation.

Perfluoropolyether (PFPE) is an industrially important fluoropolymer and has great industrial importance due to its flexible, noncombustible, and chemically robust properties. However, exploration and application of chemically modified homogeneous PFPEs are hampered by their immiscibility against nonfluorine-containing molecules. Here, the synthesis is reported of cyclic PFPE with hexaarylbiimidazoles (HABIs) in chains from linear PFPE having 2,4,5-triphenylimidazole (lophine) end groups. While phase separation between the end groups and main chains took place for linear PFPE, HABIs and main chains in cyclic PFPE are miscible to form transparent glass films. The design of cyclic PFPE also enables cyclic to linear topological transformation based on conversion of HABIs into lophines upon mild heating in the glass film state. Sequential linear-to-cyclic and cyclic-to-linear topological transformations enable fabrication of thermostabilized transparent films derived from PFPE.

Photocleavable Regenerative Network Materials with Exceptional and Repeatable Viscoelastic Manipulability.

The development of solventless system for modulating properties of network materials is imperative for the next generation sustainable technology. Utilization of photostimulation is important owing to its spatial and temporal locality, yet designing photoresponsive network materials exhibiting repeatable and dramatic change in their properties remains a challenge. Here, the authors report a photocleavable regenerative network (PRN) linked with photoresponsive hexaarylbiimidazoles (HABIs) synthesized from narrow dispersity star‐shaped poly(dimethylsiloxane)s (PDMSs) having 2,4,5‐triphenylimidazole end groups. The use of urea anion as a catalyst for ring opening polymerization (ROP) of cyclic siloxane initiated from silanols enables control of molecular weight and dispersity. The rheological measurements for the synthesized PRNs exhibit drastic changes in storage and loss moduli (G′ and G″) upon photoirradiation in the solid state (G′ > G″). This photocontrolled change in viscoelasticity with retaining solidity enables application of PRNs as a remotely‐controlled photo‐melt adhesive and photo‐scissible string. The developed PRNs will enable a wide variety of applications such as industrially important next‐generation sustainable adhesive, sealant, and reversibly‐deformable 3D printing materials with their spatially and temporally local manipulability, solventless handleability, and excellent reversibility.

Recyclable Heterogeneous Radical Generators Toward In‐Flow Polymer Elaboration System

AbstractRadical reaction is one of the most common industrial reactions for the production of materials used in a wide variety of applications. Despite its long history, a methodology enabling efficient radical reactions with safe and easy handling still remains a challenge. Here, we describe the synthesis of crosslinked copolymers containing 2,4,5‐triphenylimidazoles (lophines) and hexaarylbiimidazoles (HABIs) (CCs) and fabrication of silica‐supported CCs (s‐CCs). Both of lophines and HABIs in these materials generated 2,4,5‐triphenylimidazolyl radicals (TPIRs) upon oxidation and photoirradiation, respectively, and thus they act as heterogeneous radical generators (HRGs). Moreover, lophine and TPIR were interconvertible via oxidation and hydrogen atom transfer reaction, enabling marked recyclability of these materials. We have further packed s‐CCs in columns and realized in‐flow disulfide synthesis and radical polymerization.

Hexaarylbiimidazoles(HABI)-functionalized lyotropic liquid crystalline systems as visible light-responsive materials

Hexaarylbiimidazoles (HABIs) are a promising class of photoswitchable molecule that have received little attention in the literature. Among them, (2,2′-dimethoxydiphenylimidazole)-1,1′-binaphthyl (HABI1) displays unusual negative photochromism and is responsive to green light. This study investigates the potential of HABIs to serve as photo-responsive actuators controlling the structure of lyotropic liquid crystalline (LLC) materials. HABI1 with four methyl chains and HABI2 with four dodecyl chains were synthesized. Time resolved small angle X-ray scattering was used to characterize the potential disruptive effects of HABIs on the nanostructure of LLC systems. HABIs underwent rapid isomerization under irradiation, with a very slow reversion in the dark in toluene and in the LLC matrix, demonstrating excellent stability and photo-fatigue resistant. HABIs completely triggered phase transitions in the phytantriol-based materials, and HABI2 generated a greater disruption than HABI1 on the lipid packing due to the enhanced steric influence. Tuning the lipid composition yielded systems that transitioned from a “slow release” lamellar phase to a “burst release” bicontinuous cubic phase upon light irradiation. Such systems therefore may exhibit a triggered release behavior upon a short time of irradiation, showing great potential in “on demand” drug delivery.

Topology‐Reset Execution: Repeatable Postcyclization Recyclization of Cyclic Polymers

Repeatable topological transformation of polymers for the modulation of material functions is a challenge. We have developed a method for repeatedly resetting a cyclic macromolecular architecture to a linear architecture by photostimulation, namely, topology-reset execution (T-rex) based on the photochemistry of hexaarylbiimidazoles (HABIs). We synthesized cyclic poly(dimethylsiloxane)s (PDMSs) of various ring sizes with HABIs linked in the chains. UV irradiation of the cyclic PDMSs produced telechelic linear PDMSs with triphenylimidazolyl radical (TPIR) end groups. After termination of UV irradiation, end-to-end recyclization occurred by the recoupling of TPIRs. The cyclic PDMSs also responded to ultrasound, which decreased their molecular weight (MW) by site-specific cleavage of in-chain HABI moieties, and we are able to reset the MWs by subsequent phototriggered T-rex. Furthermore, T-rex enabled solvent-free switching of the rheological properties of the materials while retaining the liquid character of PDMS.

Topology‐Reset Execution: Repeatable Postcyclization Recyclization of Cyclic Polymers

AbstractRepeatable topological transformation of polymers for the modulation of material functions is a challenge. We have developed a method for repeatedly resetting a cyclic macromolecular architecture to a linear architecture by photostimulation, namely, topology‐reset execution (T‐rex) based on the photochemistry of hexaarylbiimidazoles (HABIs). We synthesized cyclic poly(dimethylsiloxane)s (PDMSs) of various ring sizes with HABIs linked in the chains. UV irradiation of the cyclic PDMSs produced telechelic linear PDMSs with triphenylimidazolyl radical (TPIR) end groups. After termination of UV irradiation, end‐to‐end recyclization occurred by the recoupling of TPIRs. The cyclic PDMSs also responded to ultrasound, which decreased their molecular weight (MW) by site‐specific cleavage of in‐chain HABI moieties, and we are able to reset the MWs by subsequent phototriggered T‐rex. Furthermore, T‐rex enabled solvent‐free switching of the rheological properties of the materials while retaining the liquid character of PDMS.

Hexaarylbiimidazoles as visible light thiol–ene photoinitiators

ObjectivesThe aim of this study is to determine if hexaarylbiimidazoles (HABIs) are efficient, visible light-active photoinitiators for thiol–ene systems. We hypothesize that, owing to the reactivity of lophyl radicals with thiols and the necessarily high concentration of thiol in thiol–ene formulations, HABIs will effectively initiate thiol–ene polymerization upon visible light irradiation. MethodsUV–vis absorption spectra of photoinitiator solutions were obtained using UV–vis spectroscopy, while EPR spectroscopy was used to confirm radical species generation upon HABI photolysis. Functional group conversions during photopolymerization were monitored using FTIR spectroscopy, and thermomechanical properties were determined using dynamic mechanical analysis. ResultsThe HABI derivatives investigated exhibit less absorptivity than camphorquinone at 469nm; however, they afford increased sensitivity at this wavelength when compared with bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. Photolysis of the investigated HABIs affords lophyl radicals. Affixing hydroxyhexyl functional groups to the HABI core significantly improved solubility. Thiol–ene resins formulated with HABI photoinitiators polymerized rapidly upon irradiation with 469nm. The glass transition temperatures of the thiol–ene resin formulated with a bis(hydroxyhexyl)-functionalized HABI and photopolymerized at room and body temperature were 49.5±0.5°C and 52.2±0.1°C, respectively. SignificanceAlthough thiol–enes show promise as continuous phases for composite dental restorative materials, they show poor reactivity with the conventional camphorquinone/tertiary amine photoinitiation system. Conversely, despite their relatively low visible light absorptivity, HABI photoinitiators afford rapid thiol–ene photopolymerization rates. Moreover, minor structural modifications suggest pathways for improved HABI solubility and visible light absorption.