Achieving Sub-ppm Sensitivity in SO2 Detection with a Chemically Stable Covalent Organic Framework.

We report the inaugural experimental investigation of covalent organic frameworks (COFs) to address the formidable challenge of SO2 detection. Specifically, an imine-functionalized COF (SonoCOF-9) demonstrated a modest and reversible SO2 sorption of 3.5 mmol g-1 at 1 bar and 298 K. At 0.1 bar (and 298 K), the total SO2 uptake reached 0.91 mmol g-1 with excellent reversibility for at least 50 adsorption-desorption cycles. An isosteric enthalpy of adsorption (ΔHads) for SO2 equaled -42.3 kJ mol-1, indicating a relatively strong interaction of SO2 molecules with the COF material. Also, molecular dynamics simulations and Møller-Plesset perturbation theory calculations showed the interaction of SO2 with π density of the rings and lone pairs of the N atoms of SonoCOF-9. The combination of experimental data and theoretical calculations corroborated the potential use of this COF for the selective detection and sensing of SO2 at the sub-ppm level (0.0064 ppm of SO2).

CYCU-3: an Al(III)-based MOF for SO2 capture and detection.

The Al(III)-based MOF CYCU-3 exhibits a relevant SO2 adsorption performance with a total uptake of 11.03 mmol g-1 at 1 bar and 298 K. CYCU-3 displays high chemical stability towards dry and wet SO2 exposure. DRIFTS experiments and computational calculations demonstrated that hydrogen bonding between SO2 molecules and bridging Al(III)-OH groups are the preferential adsorption sites. In addition, photoluminescence experiments demonstrated the relevance of CYCU-3 for application in SO2 detection with good selectivity for SO2 over CO2 and H2O. The change in fluorescence performance demonstrates a clear turn-on effect after SO2 interaction. Finally, the suppression of ligand-metal energy transfer along with the enhancement of ligand-centered π* → π electronic transition was proposed as a plausible fluorescence mechanism.

Surfactant-tail control of CsPbBr3 nanocrystal morphology.

CsPbBr3 nanocrystals (NCs) are promising optoelectronic and catalytic materials. Manipulating their morphology can improve their properties and stability. In this work, an alkene-derived zwitterionic ligand was used to control the morphology of CsPbBr3 NCs to yield the highly unusual rhombicuboctahedron morphology, showcasing the first example of a surfactant-tail controlled growth.

Detection of SO2 using a chemically stable Ni(II)-MOF.

The MOF-type Ni2(dobpdc) shows a high chemical stability towards SO2, high capacity for SO2 capture at low pressure (4.3 mmol g-1 at 298 K and up to 0.05 bar), and exceptional cycling performance. Fluorescence experiments demonstrated the SO2 detection properties of Ni2(dobpdc) with a remarkable SO2 detection selectivity. Finally, time-resolved photoluminescence experiments provided a plausible mechanism of SO2 detection by this Ni(II)-based MOF material.

Modulated self-assembly of three flexible Cr(III) PCPs for SO2 adsorption and detection.

Modulated self-assembly protocols are used to develop facile, HF-free syntheses of the archetypal flexible PCP, MIL-53(Cr), and novel isoreticular analogues MIL-53(Cr)-Br and MIL-53(Cr)-NO2. All three PCPs show good SO2 uptake (298 K, 1 bar) and high chemical stabilities against dry and wet SO2. Solid-state photoluminescence spectroscopy indicates all three PCPs exhibit turn-off sensing of SO2, in particular MIL-53(Cr)-Br, which shows a 2.7-fold decrease in emission on exposure to SO2 at room temperature, indicating potential sensing applications.

Pairing multicomponent stators with aromatic rotators for new emissive molecular rotors.

We demonstrate here that the Ugi-Sonogashira protocol can be successfully used to obtain five new molecular rotors 10a-e with strong emission. They have been synthesized by combining multicomponent Ugi stators and several aromatic rotary components: phenylene, p-xylene, naphthalene and anthracene. The synthesized conjugated rotors are highly fluorescent (Φf = 0.39 to Φf = 0.10), and changes in their emission were observed upon variations of the surrounding media. Particularly, we found that they are sensitive to aggregation (THF/water) or high viscosity (methanol/glycerol) conditions. This work paves the way to develop new emissive rotors with exciting photophysical properties.

Multicomponent synthesis and anti-proliferative screening of biaryl triazole-containing cyclophanes.

We report a practical two-step approach involving a Ugi 4-CR/ azide-alkyne cycloaddition for the synthesis of biaryl-containing cyclophanes. The series represents an extension of our previously reported macrocycles as an effort to enhance the anti-proliferative activity of this scaffold. In this variant, we incorporate a biphenyl moiety in the framework, thus enhancing the macrocycle size, lipophilicity, and structural diversity. Macrocycles were tested against different cell lines, being more cytotoxic against prostate (PC-3 and DU-145) and breast (MCF-7) tumor cells. Gratifyingly, the most active compound showed a significative enhancement of PC-3 growth inhibition with respect to our previous series, reaffirming the potential anti-proliferative activity of this kind of cyclophanes.

Diversity-Oriented Synthesis of Highly Fluorescent Fused Isoquinolines for Specific Subcellular Localization.

A multicomponent diversity-oriented synthesis of new highly emissive tetracyclic isoquinolines that target specific organelles is described. The title compounds were prepared via a three-step protocol starting with an Ugi four-component reaction, followed by either an intramolecular alkyne hydroarylation and subsequent alkene isomerization or through a Pomeranz-Fritsch-type cyclization with a final intramolecular Heck reaction. Subcellular localization studies of these compounds using green channel confocal microscopy revealed remarkable and distinctive distribution patterns in live cells, showing an unprecedented high selectivity and imaging contrast. The differentiated organelle visualization-including localizers for mitochondria, lysosomes, Golgi apparatus, endoplasmic reticulum, and plasma membrane-was achieved by varying the nature of the tetracyclic system and substituent pattern, changing the original four-component set in the starting Ugi reaction.

Synthesis of 6-methyl-3,4-dihydropyrazinones using an Ugi 4-CR/allenamide cycloisomerization protocol.

A synthetic approach to the 6-methyl-3,4-dihydropyrazinone core from Ugi adducts is described. This methodology relies on the regioselective C-N bond formation between an allenamide moiety at C-ß and an amide anion formed under base-mediated conditions. This protocol allows easy access to tricyclic systems such as pyrazino[2,1-a]isoindole and pyrazino[2,1-a]isoquinoline nuclei.