Producing ultra-stabilized radicals via light irradiation has raised considerable concern but remains a tremendous challenge in functional materials. Herein, optically actuating ultra-stable radicals are discovered in a sterically encumbered and large πconjugated tri(4-pyridyl)-1,3,5-triazine (TPT) ligands constructed photochromic compound Cu 3 (H-HEDP) 2 TPT 2 •2H 2 O (QDU-12; HEDP=hydroxyethylidene diphosphonate). The photogeneration of TPT• radicals is the photoactive behavior of electron transfer from HEDP motifs to TPT units. The ultra-long-lived radicals are contributed from strong interchain π-π interactions between the large π-conjugated TPT components, with the radical lifetime maintained for about 18 months under ambient conditions. Moreover, the antiferromagnetic couplings between TPT • radicals and Cu 2+ ions plummeted the demagnetization to 35% of its original state after light irradiation, showing the largest room temperature photodemagnetization in the current radicalbased photochromic materials.
Intraoperative application of ketamine was associated with improved scores for depressed mood and increased serum BDNF levels in patients undergoing elective orthopedic surgery.
Abstract:In order to discover new compounds with good fungicidal activities, 32 pyrazole derivatives were designed and synthesized. The structures of the target compounds were confirmed by 1 H-NMR, 13 C-NMR, and high-resolution electrospray ionization mass spectrometry (HR-ESI-MS), and their fungicidal activities against Botrytis cinerea, Rhizoctonia solani Kuhn, Valsa mali Miyabe et Yamada, Thanatephorus cucumeris (Frank) Donk, Fusarium oxysporum (S-chl) f.sp. cucumerinum Owen, and Fusarium graminearum Schw were tested. The bioassay results indicated that most of the derivatives exhibited considerable antifungal activities, especially compound 26 containing a p-trifluoromethylphenyl moiety showed the highest activity, with EC 50 values of 2.432, 2.182, 1.787, 1.638, 6.986, and 6.043 μg/mL against B. cinerea, R. solani, V. mali, T. cucumeris, F. oxysporum, and F. graminearum, respectively. Moreover, the activities of compounds such as compounds 27-32 were enhanced by introducing isothiocyanate and carboxamide moieties to the 5-position of the pyrazole ring.
Incorporating heterometal and chromogenic
groups into the titanium
oxo cluster (TOC) nanomaterials is one of the effective strategies
for the development of new high-performance photoelectrically active
materials. In this Article, we report the structures and photoelectrochemical
(PEC) performances of a family of TOCs, including pure [Ti12O8(OEt)16L8] ({Me-Ti
12
}) and six Cd-doped clusters
formulated as [H4Cd2Ti10O8(OEt)16(L)8(H2O)2] ({Cd
2
Ti
10
}; L = salicylic acid and their derivatives).
The six Cd-doped clusters are isostructural, containing the same {Cd2Ti10O8} core, but are protected by salicylic
ligands modified with different functional groups. The compositions,
structures, and solution stability of these clusters have been studied
in detail by single-crystal X-ray diffraction and electrospray ionization
mass spectrometry measurements. The embedding of heterometallic Cd(II)
and chemical modification of organic protective shells can effectively
regulate the PEC water oxidation activity of those clusters, with {F-Cd
2
Ti
10
} having the highest turnover number of 518.55
and the highest turnover frequency of 172.85 h–1. Our work highlights the potential of using TOCs that do not contain
noble metals as water oxidation catalysts, and their catalytic activity
can be regulated by structural modification.
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