Three emissive bridged-triphenylamine derivatives are designed and synthesized by incorporating carbon (DQAO), oxygen (OQAO), and sulfur (SQAO) atoms with two carbonyl groups. The fully bridged geometry and unique frontier molecular orbital distribution reveal its potential as narrowband thermally activated delayed fluorescence emitters. DQAO-, OQAO-, and SQAO-based organic light-emitting diodes exhibit the maximum external quantum efficiency (EQEmax) of 15.2%, 20.3%, and 17.8% for blue, green, and yellow, respectively.In lithium-organic batteries, organic cathode materials could dissolve in a liquid electrolyte and diffuse through the porous separator to the active lithium-metal anode, resulting in cycling instability. However, 2,2'-dipyridyl disulfide (PyDS) can be cycled 5 times better than diphenyl disulfide (PDS) although both are soluble. We believe this is related to their reactivity with lithium (Li0). Herein, we investigate the chemical reduction of PyDS by lithiated carbon paper (Li-CP) in ether electrolyte. It is found that only 6.3% of PyDS was reduced by Li-CP after 10 days, unlike PDS. Experimental and computational results show that PyDS molecules are ionized by lithium ions of lithium salts delocalizing the charge on pyridine rings of PyDS, which can momentarily store Li0, thus keeping the S-S bond inert in chemical reaction with Li0. This finding is successfully utilized in a membrane-free redox flow battery with PyDS catholyte, showing long cycle life with high energy density and energy efficiency. This work reveals the interesting charge storage mechanism and the different activity of organodisulfides toward electrochemical reduction and chemical reduction due to the organic groups, which can provide guidance for the design of stable lithium-organic batteries.Methods to activate the relatively stable ether C-O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C-O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered less then -2.6 V vs SCE), this mode of ether C-O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C-O bond using a carbazole-based organic photocatalyst (PC). https://www.selleckchem.com/HSP-90.html Both benzylic and non-benzylic aryl ethers underwent C-O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N-H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N-H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.Catalyzed by silver salt, the unactivated C(sp3)-H heteroarylation of free alcohol at the δ position is realized under gentle thermal conditions in water through a radical procedure. Both protonic acids and Lewis acids are found to be efficient for activating pyridines for this Minisci-type reaction. The reaction enjoys a good functional group tolerance and substrate scope. Terminal secondary and tertiary alcohols are suitable substrates. With either electron-donating or -withdrawing groups, the electron-deficient heteroarene substrates generate the target products in moderate to good yields. A gram-scale experiment can be successfully operated. A radical blocking experiment and a radical clock experiment are studied to support the radical mechanism.Upon treatment with a Lewis base catalyst, β-alkyl-substituted nitroalkenes could be readily converted into allylic nitro compounds. Examples of either C-1 or C-3 functionalization methods have been reported through nitro-elimination, giving alkene products. In this work, successful 1,3-difunctionalization was achieved through a synergetic Lewis base catalysis and TBHP radical oxidation, giving vinylic alkoxyamines in good to excellent yields. This work further extended the general synthetic application of β-alkyl nitroalkenes.Benziodoxole triflate (BXT), a cyclic iodine(III) electrophile, has been found to promote a rearrangement of propargylic alcohols into α,β-unsaturated ketones bearing an α-λ3-iodanyl group. This iodo(III)-Meyer-Schuster rearrangement proceeds under mild conditions and tolerates a variety of functionalized propargylic alcohols, thus complementing previously reported halogen-intercepted Meyer-Schuster rearrangement. The α-λ3-iodanylenones can be utilized for facile Pd-catalyzed cross-coupling for the synthesis of multisubstituted enones.Lipid nanoparticles (LNPs) containing short-interfering RNA (LNP-siRNA systems) are a promising approach for silencing disease-causing genes in hepatocytes following intravenous administration. LNP-siRNA systems are generated by rapid mixing of lipids in ethanol with siRNA in aqueous buffer (pH 4.0) where the ionizable lipid is positively charged, followed by dialysis to remove ethanol and to raise the pH to 7.4. Ionizable cationic lipids are the critical excipient in LNP systems as they drive entrapment and intracellular delivery. A recent study on the formation of LNP-siRNA systems suggested that ionizable cationic lipids segregate from other lipid components upon charge neutralization to form an amorphous oil droplet in the core of LNPs. This leads to a decrease in intervesicle electrostatic repulsion, thereby engendering fusion of small vesicles to form final LNPs of increased size. In this study, we prepared LNP-siRNA systems containing four lipid components (hydrogenated soy phosphatidylcholine, cholestnt and manufacturing conditions for LNP-siRNA systems.An unprecedented C(CO)-C(Ar) bond cleavage of β-enaminones has been realized under mild and transition-metal-free conditions. The cascade transformation based on this C-C bond cleavage involves 1,3-O/C migration and aerobic hydroxylation and leads to various 5-hydroxy-1H-pyrrol-2(5H)-ones with broad functional group tolerance. The application of this methodology has been showcased by preparing 5-alkoxy-1H-pyrrol-2(5H)-one derivatives and a pyrrolo[2,1-a]isoquinolin-3-one derivative.
Three emissive bridged-triphenylamine derivatives are designed and synthesized by incorporating carbon (DQAO), oxygen (OQAO), and sulfur (SQAO) atoms with two carbonyl groups. The fully bridged geometry and unique frontier molecular orbital distribution reveal its potential as narrowband thermally activated delayed fluorescence emitters. DQAO-, OQAO-, and SQAO-based organic light-emitting diodes exhibit the maximum external quantum efficiency (EQEmax) of 15.2%, 20.3%, and 17.8% for blue, green, and yellow, respectively.In lithium-organic batteries, organic cathode materials could dissolve in a liquid electrolyte and diffuse through the porous separator to the active lithium-metal anode, resulting in cycling instability. However, 2,2'-dipyridyl disulfide (PyDS) can be cycled 5 times better than diphenyl disulfide (PDS) although both are soluble. We believe this is related to their reactivity with lithium (Li0). Herein, we investigate the chemical reduction of PyDS by lithiated carbon paper (Li-CP) in ether electrolyte. It is found that only 6.3% of PyDS was reduced by Li-CP after 10 days, unlike PDS. Experimental and computational results show that PyDS molecules are ionized by lithium ions of lithium salts delocalizing the charge on pyridine rings of PyDS, which can momentarily store Li0, thus keeping the S-S bond inert in chemical reaction with Li0. This finding is successfully utilized in a membrane-free redox flow battery with PyDS catholyte, showing long cycle life with high energy density and energy efficiency. This work reveals the interesting charge storage mechanism and the different activity of organodisulfides toward electrochemical reduction and chemical reduction due to the organic groups, which can provide guidance for the design of stable lithium-organic batteries.Methods to activate the relatively stable ether C-O bonds and convert them to other functional groups are desirable. One-electron reduction of ethers is a potentially promising route to cleave the C-O bond. However, owing to the highly negative redox potential of alkyl aryl ethers (Ered less then -2.6 V vs SCE), this mode of ether C-O bond activation is challenging. Herein, we report the visible-light-induced photocatalytic cleavage of the alkyl aryl ether C-O bond using a carbazole-based organic photocatalyst (PC). https://www.selleckchem.com/HSP-90.html Both benzylic and non-benzylic aryl ethers underwent C-O bond cleavage to form the corresponding phenol products. Addition of Cs2CO3 was beneficial, especially in reactions using a N-H carbazole PC. The reaction was proposed to occur via single-electron transfer (SET) from the excited-state carbazole to the substrate ether. Interaction of the N-H carbazole PC with Cs2CO3 via hydrogen bonding exists, which enables a deprotonation-assisted electron-transfer mechanism to operate. In addition, the Lewis acidic Cs cation interacts with the substrate alkyl aryl ether to activate it as an electron acceptor. The high reducing ability of the carbazole combined with the beneficial effects of Cs2CO3 made this otherwise formidable SET event possible.Catalyzed by silver salt, the unactivated C(sp3)-H heteroarylation of free alcohol at the δ position is realized under gentle thermal conditions in water through a radical procedure. Both protonic acids and Lewis acids are found to be efficient for activating pyridines for this Minisci-type reaction. The reaction enjoys a good functional group tolerance and substrate scope. Terminal secondary and tertiary alcohols are suitable substrates. With either electron-donating or -withdrawing groups, the electron-deficient heteroarene substrates generate the target products in moderate to good yields. A gram-scale experiment can be successfully operated. A radical blocking experiment and a radical clock experiment are studied to support the radical mechanism.Upon treatment with a Lewis base catalyst, β-alkyl-substituted nitroalkenes could be readily converted into allylic nitro compounds. Examples of either C-1 or C-3 functionalization methods have been reported through nitro-elimination, giving alkene products. In this work, successful 1,3-difunctionalization was achieved through a synergetic Lewis base catalysis and TBHP radical oxidation, giving vinylic alkoxyamines in good to excellent yields. This work further extended the general synthetic application of β-alkyl nitroalkenes.Benziodoxole triflate (BXT), a cyclic iodine(III) electrophile, has been found to promote a rearrangement of propargylic alcohols into α,β-unsaturated ketones bearing an α-λ3-iodanyl group. This iodo(III)-Meyer-Schuster rearrangement proceeds under mild conditions and tolerates a variety of functionalized propargylic alcohols, thus complementing previously reported halogen-intercepted Meyer-Schuster rearrangement. The α-λ3-iodanylenones can be utilized for facile Pd-catalyzed cross-coupling for the synthesis of multisubstituted enones.Lipid nanoparticles (LNPs) containing short-interfering RNA (LNP-siRNA systems) are a promising approach for silencing disease-causing genes in hepatocytes following intravenous administration. LNP-siRNA systems are generated by rapid mixing of lipids in ethanol with siRNA in aqueous buffer (pH 4.0) where the ionizable lipid is positively charged, followed by dialysis to remove ethanol and to raise the pH to 7.4. Ionizable cationic lipids are the critical excipient in LNP systems as they drive entrapment and intracellular delivery. A recent study on the formation of LNP-siRNA systems suggested that ionizable cationic lipids segregate from other lipid components upon charge neutralization to form an amorphous oil droplet in the core of LNPs. This leads to a decrease in intervesicle electrostatic repulsion, thereby engendering fusion of small vesicles to form final LNPs of increased size. In this study, we prepared LNP-siRNA systems containing four lipid components (hydrogenated soy phosphatidylcholine, cholestnt and manufacturing conditions for LNP-siRNA systems.An unprecedented C(CO)-C(Ar) bond cleavage of β-enaminones has been realized under mild and transition-metal-free conditions. The cascade transformation based on this C-C bond cleavage involves 1,3-O/C migration and aerobic hydroxylation and leads to various 5-hydroxy-1H-pyrrol-2(5H)-ones with broad functional group tolerance. The application of this methodology has been showcased by preparing 5-alkoxy-1H-pyrrol-2(5H)-one derivatives and a pyrrolo[2,1-a]isoquinolin-3-one derivative.
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