Ambient-Light-Promoted Stereospecific Synthesis of (Z)-Vinyl Thioesters under Solvent- and Catalyst-Free Conditions.

An ambient-light-promoted stereospecific olefinic C(sp2)-S bond construction of thioacids and 1,1-diarylethenes has been demonstrated, affording various (Z)-vinyl thioesters in 51-85% yields under solvent- and catalyst-free conditions. Mechanistic studies indicated that the formation of thioacid-olefin complexes is responsible for generating a carbonyl thiyl radical and dioxygen in the air participates in the reaction and functions as a traceless reagent. Moreover, synthetic applications have been demonstrated by the gram scale synthesis and aggregation-induced emission property of representative compound 3i.

Design principle of half-sandwich type erbium single-ion magnets through crystal field engineering: a combined magnetic and electronic structure study.

To conclude the design principle for high-performance erbium-based single-ion magnets (SIMs), two half-sandwich type erbium complexes 1Er [(LOMe)Er(COT)] (LOMe = [(η5-C5H5)Co{P([double bond, length as m-dash]O)(OMe)2}3], COT = cyclooctatetraenyl) and 2Er [(THF)2(OAr)Er(COT)] (Ar = 2,6-Dipp2C6H3, Dipp = 2,6-diisopropylphenyl) were synthesized, and structurally and magnetically characterized. Both of them exhibited SIM behavior. Their magnetic relaxation behaviours were further elucidated by ab initio calculations and near-IR emission spectroscopy. The results demonstrated that an axial ligand with a weaker electron-donating effect was preferential to construct high blocking barrier erbium-based SIMs.

Micro-flow nanocatalysis: synergic effect of TfOH@SPIONs and micro-flow technology as an efficient and robust catalytic system for the synthesis of plasticizers.

The combination of continuous flow technology with immobilizing of only 0.13 mol% of triflic acid (TfOH) on silica-encapsulated superparamagnetic iron oxide nanoparticles (SPIONs) under solvent-free conditions successfully provided a powerful, efficient, and eco-friendly route for the synthesis of plasticizers. The turnover frequency value in micro-flow conditions varied in the range of 948.7 to 7384.6 h-1 compared to 403.8 to 3099 h-1 for in-flask. This technique works efficiently, encouraging future applications of micro-flow nano-catalysis in green chemistry.

Highly near-IR emissive ytterbium(iii) complexes with unprecedented quantum yields.

The design of highly near-infrared (NIR) emissive lanthanide (Ln) complexes is challenging, owing to the lack of molecular systems with a high sensitization efficiency and the difficulty of achieving a large intrinsic quantum yield. Previous studies have reported success in optimizing individual factors and achieving high overall quantum yields, with the best yield being 12% for Yb(iii). Herein we report a series of highly NIR emissive Yb complexes, in which the Yb is sandwiched between an octafluorinated porphyrinate antenna ligand and a deuterated Kläui ligand, which allowed optimization of two factors in the same system, and one of the complexes had an unprecedented quantum yield of 63% (estimated uncertainty 15%) in CD2Cl2 with a long lifetime (τobs) of 714 µs. Systematic analysis of the structure-photophysical properties relationship suggested that porphyrinates are effective antenna ligands with a sensitization efficiency up to ca. 100% and that replacement of the high-energy C-H oscillators in porphyrinate and Kläui ligands significantly improves the intrinsic quantum yield up to 75% (τobs/τrad), both of which contribute to enhancing the NIR emission intensity of Yb(iii) up to 25-fold. Besides the high luminescence efficiency, these Yb complexes have other attractive features such as excitation in the visible range and large extinction coefficients which make these Yb(iii) complexes outstanding optical materials in the NIR region.

Bioinspired Orientation of ß-Substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity.

"Configurational isomerism" is an important approach found in naturally occurring chlorophylls to modulate light harvesting function without significant structural changes; however, this feature has been seldom applied in design of antenna ligands for lanthanide (Ln) sensitization. In this work, we introduced a bioinspired approach by orientation of ß-dilactone moieties on porphyrinates, namely cis-/trans-porphodilactones, to modulate the energy transfer process from the lowest triplet excited state of the ligand (T1) to the emitting level of ytterbium(III) (2F5/2, Yb*). Interestingly, near-infrared (NIR) emission of Yb(III) could be switched "on" by the cis-porphodilactone ligand, while the trans-isomer renders Yb(III) emission "off" and the ratio of quantum yields is ∼8. Analysis of the structure-photophysical properties relationship suggests that the significant emission difference is correlated to the energy gaps between T1 and Yb* (1152 cm-1 in the cis- vs -25 cm-1 in the trans-isomer). More interestingly, due to back energy transfer (BEnT), the Yb(III) complex of cis-porphodilactone exhibits NIR emission with high thermosensitivity (4.0%°C-1 in solution and 4.9%°C-1 in solid state), comparable to previously reported terbium (Tb) and europium (Eu) visible emitters, in contrast to the trivial emission changes of the trans-isomer and porphyrin and porpholactone analogues. This work opens up new access to design NIR emissive Ln complexes by bioinspired modification of antenna ligands.

Gadolinium(III) Porpholactones as Efficient and Robust Singlet Oxygen Photosensitizers.

Construction of Gd(III) photosensitizers is important for designing theranostic agents owing to the unique properties arising from seven unpaired f electrons of the Gd(3+) ion. Combining these with the advantages of porpholactones with tunable NIR absorption, we herein report the synthesis of Gd(III) complexes Gd-1-4 (1, porphyrin; 2, porpholactone; 3 and 4, cis- and trans-porphodilactone, respectively) and investigated their function as singlet oxygen ((1) O2 ) photosensitizers. These Gd complexes displayed (1) O2 quantum yields (ΦΔ s) from 0.64-0.99 with the order Gd-1

Constructing a Catalytic Cycle for C-F to C-X (X = O, S, N) Bond Transformation Based on Gold-Mediated Ligand Nucleophilic Attack.

A tricoordinated gold(I) chloride complex, tBuXantphosAuCl, supported by a sterically bulky 9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene ligand (tBuXantphos) was synthesized. This complex features a remarkably longer Au-Cl bond length [2.632(1) Å] than bicoordinated linear gold complexes (2.27-2.30 Å) and tricoordinated XantphosAuCl [2.462(1) Å]. Single-crystal X-ray diffraction analysis of a cocrystal of tBuXantphosAuCl and pentafluoronitrobenzene (PFNB) and UV-vis spectroscopic titration experiments revealed the existence of an anion-π interaction between the Cl anion ligand and PFNB. Stoichiometric reaction between PFNB and tBuXantphosAuOtBu, after replacement of Cl by a more nucleophilic tBuO anion ligand, showed higher reactivity and para selectivity in the transformation of C-F to C-OtBu bond, distinctively different from that when only KOtBu was used (ortho selectivity) under the identical condition. Mechanistic studies including density functional theory calculations suggested a gold-mediated nucleophilic ligand attack of the C-F bond pathway via an SNAr process. On the basis of these results, using trimethylsilyl derivatives TMS-X (X = OMe, SEt, NEt2) as the nucleophilic ligand source and the fluorine acceptor, catalytic transformation of the C-F bond of aromatic substrates to the C-X (X = O, S, N) bond was achieved with tBuXantphosAuCl as the catalyst (up to 20 turnover numbers).