Having a compact yet robust structurally based identifier or representation system is key enabling factor for efficient sharing and dissemination of research results within the chemistry community, such systems lay down essential foundations future informatics data-driven research. While substantial advances have been made small molecules, polymer community has struggled in coming up with an system. This because, unlike other disciplines chemistry, basic premise that each distinct chemical...

This paper describes reversible "on–off" switching of the photoluminescence (PL) intensity CdSe quantum dots (QDs), mediated by photochromic furylfulgide carboxylate (FFC) molecules chemisorbed to surfaces QDs. Repeated cycles UV and visible illumination switch FFC between "closed" "open" isomers. Reversible QDs' PL >80% is enabled different rates yields PL-quenching photoinduced electron transfer (PET) from QDs respective difference consistent with cyclic voltammetry measurements density...

Abstract π‐Conjugated polymers (CPs) combine the flexibility, processability, and lightness of plastics with semiconducting properties for optoelectronic applications. These are conventionally synthesized by thermal transition‐metal‐catalyzed polycondensation. Photochemical approaches to CPs offer possibility direct photopatterning, but present mechanistic challenges. Shimidzu first described photopolymerization thiophene derivatives in 1990s, field lay dormant many years. Recently, both...

Current approaches to synthesize π-conjugated polymers (CPs) are dominated by thermally driven, transition-metal-mediated reactions. Herein we show that electron-deficient Grignard monomers readily polymerize under visible-light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned wavelength based on absorption polymer. Conversion studies consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces...

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis n-type π-conjugated polymers. Herein, we describe an experimental computational investigation into mechanism this photopolymerization. Spectroscopic studies performed...

Abstract Current approaches to synthesize π‐conjugated polymers (CPs) are dominated by thermally driven, transition‐metal‐mediated reactions. Herein we show that electron‐deficient Grignard monomers readily polymerize under visible‐light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned wavelength based on absorption polymer. Conversion studies consistent with an uncontrolled chain‐growth process; correspondingly, chain extension produces...

Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition metal-mediated methods. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned wavelength based on absorption polymer. Conversion studies consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces all-conjugated...

Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition metal-mediated methods. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned wavelength based on absorption polymer. Conversion studies consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces all-conjugated...

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis n-type π-conjugated polymers. Herein we provide an experimental computational investigation mechanism this photopolymerization. Spectroscopic studies performed situ...

Dithioalkylidenes are a recently-developed class of conjugate acceptors that undergo thiol exchange via an associative mechanism and have been used for reprocessable vitrimers, amine sensors, degradable networks. Here, we show the rate reaction in aqueous environments is highly sensitive to structure acceptor may be varied over four orders magnitude. Cyclic rapidly, from 0.95 15.6 M-1s-1, while acyclic between 3.77x10-3 2.17x10-2 M-1s-1. Computational, spectroscopic, structural data suggest...

Dithioalkylidenes are a newly-developed class of conjugate acceptors that undergo thiol exchange via an associative mechanism, enabling decoupling key material properties for sustainability, biomedical, and sensing applications. Here, we show the rate reaction in aqueous environments is highly sensitive to structure acceptor tunable over four orders magnitude. Cyclic rapidly, from 0.95 15.6 M-1s-1, while acyclic between 3.77x10-3 2.17x10-2 M-1s-1

Silicon (Si) anode has tremendous potential for the next-generation high energy density lithium-ion battery, but development of devices with sufficient capacity retention and calendar life remains elusive. While numerous studies have characterized composition dynamics solid-electrolyte-interface (SEI) on silicon anodes, chemical mechanisms that produce identified species remain largely speculative conflicting. In this presentation, we demonstrate use trimethylsilyllithium as a model compound...

Current approaches to synthesize π-conjugated polymers are dominated by thermally driven, transition metal-mediated methods. Herein we show that electron-deficient Grignard monomers readily polymerize under visible light irradiation at room temperature in the absence of a catalyst. The product distribution can be tuned wavelength based on absorption polymer. Conversion studies consistent with an uncontrolled chain-growth process; correspondingly, chain extension produces blocky...

Substrate-selective reactions typically rely on differences in the ground-state reactivity of substrates or their interactions with supramolecular catalyst scaffolds. Here, we show that a photoinduced cross-coupling reaction provides high substrate selectivity cannot be achieved under thermal conditions. We report visible-light-promoted, Ni-catalyzed Suzuki–Miyaura diiodo-boron-dipyrromethene (BODIPY) chromophores displaying for mono-arylation, enabling efficient sequential synthesis...

Metallaphotoredox catalysis combines the well-established mechanisms of transition-metal-catalyzed cross-coupling reactions with one-electron redox manipulations enabled by light. In most cases, a transition metal or organic dye serves as photoredox catalyst while ground-state Pd Ni performs organometallic steps. Cross-coupling that rely on direct photoexcitation light-absorbing substrate have potential to access distinct and deliver unique selectivity based substrate’s excited-state...

Metallaphotoredox catalysis combines the well-established mechanisms of transition-metal-catalyzed cross-coupling reactions with one-electron redox manipulations enabled by light. In most cases, a transition metal or organic dye serves as photoredox catalyst while ground-state Pd Ni performs organometallic steps. Cross-coupling that rely on direct photoexcitation light-absorbing substrate have potential to access distinct and deliver unique selectivity based substrate’s excited-state...

π-Conjugated polymers can serve as active layers in flexible and lightweight electronics, are conventionally synthesized by transition-metal-mediated polycondensation at elevated temperatures. We recently reported a photopolymerization of electron-deficient heteroaryl Grignard monomers that enables the catalyst-free synthesis n-type π-conjugated polymers. Herein we provide an experimental computational investigation mechanism this photopolymerization. Spectroscopic studies performed...