Reversible‐deactivation radical polymerizations (RDRPs) have revolutionized synthetic polymer chemistry. Nowadays, RDRPs facilitate design and preparation of materials with controlled architecture, composition, and functionality. Atom transfer radical polymerization (ATRP) has evolved beyond traditional polymer field, enabling synthesis of organic–inorganic hybrids, bioconjugates, advanced polymers for electronics, energy, and environmentally relevant polymeric materials for broad applications in various fields. This review focuses on the relation between ATRP technology and the 12 principles of green chemistry, which are paramount guidelines in sustainable research and implementation. The green features of ATRP are presented, discussing the environmental and/or health issues and the challenges that remain to be overcome. Key discoveries and recent developments in green ATRP are highlighted, while providing a perspective for future opportunities in this area.

Optically active luminescent materials based on lanthanide ions attract significant attention due to their unique spectroscopic properties, nonlinear optical activity, and the possibility of application as contactless sensors. Lanthanide metal-organic frameworks (Ln-MOFs) that exhibit strong second-harmonic generation (SHG) and are optically active in the NIR region are unexpectedly underrepresented. Moreover, such Ln-MOFs require ligands that are chiral and/or need multistep synthetic procedures. Here, we show that the NIR pulsed laser irradiation of the noncentrosymmetric, isostructural Ln-MOF materials (MOF-Er³⁺ (1) and codoped MOF-Yb³⁺/Er³⁺ (2)) that are constructed from simple, achiral organic substrates in a one-step procedure results in strong and tunable SHG activity. The SHG signals could be easily collected, exciting the materials in a broad NIR spectral range, from ≈800 to 1500 nm, resulting in the intense color of emission, observed in the entire visible spectral region. Moreover, upon excitation in the range of ≈900 to 1025 nm, the materials also exhibit the NIR luminescence of Er³⁺ ions, centered at ≈1550 nm. The use of a 975 nm pulse excitation allows simultaneous observations of the conventional NIR emission of Er³⁺ and the SHG signal, altogether tuned by the composition of the Ln-MOF materials. Taking the benefits of different thermal responses of the mentioned effects, we have developed a nonlinear optical thermometer based on lanthanide-MOF materials. In this system, the SHG signal decreases with temperature, whereas the NIR emission band of Er³⁺ slightly broadens, allowing ratiometric (Er³⁺ NIR 1550 nm/SHG 488 nm) temperature monitoring. Our study provides a groundwork for the rational design of readily available and self-monitoring NLO-active Ln-MOFs with the desired optical and electronic properties.

The unique electrochemical properties of polyoxometalates (POMs) render them ideal components for the fabrication of next‐generation high‐performance energy storage systems. However, their practical applications have been hindered by their high solubility in common electrolytes. This problem can be overcome by the effective hybridization of POMs with other materials. Here we present the design and synthesis of two novel polyoxometalate‐covalent organic frameworks (POCOF) via one‐pot solvothermal strategy between an amino‐functionalized Anderson‐type POM and a trialdehyde‐based building unit. We show that structural and functional complexity can be enriched by adding hydroxyl groups in the 2,4,6 position to the benzene‐1,3,5‐tricarbaldehyde allowing to exploit for the first time in POCOFs the keto‐enol tautomerization as additional feature to impart greater chemical stability to the COFs and enhanced properties leading to large specific surface area (347 m²/g) and superior electrochemical performance of the POCOF‐1 electrodes, when compared with POCOF‐2 electrodes that possess only imine‐type linkage and with pristine POM electrodes. Specifically, POCOF‐1 electrodes display remarkable specific, areal, and volumetric capacitance (125 F/g, 248 mF/cm² and 41.9 mF/cm³, respectively) at a current density of 0.5 A/g, a maximum energy density (56.2 Wh/kg), a maximum power density (3.7 kW/kg) and an outstanding cyclability (90 % capacitance retention after 5000 cycles).

Photomediated Atom Transfer Radical Polymerization (photoATRP) is an activator regeneration method, which allows for the controlled synthesis of well‐defined polymers via light irradiation. Traditional photoATRP is often limited by the need for high‐energy ultraviolet or violet light. These could negatively affect the control and selectivity of the polymerization, promote side reactions, and may not be applicable to biologically relevant systems. This drawback can be circumvented by an introduction of the catalytic amount of photocatalysts, which absorb visible and/or NIR light and, therefore, controlled, regenerative ATRP can be performed with the dual‐catalytic cycle. Herein, a critical summary of recent developments in the field of dual‐catalysis concerning Cu‐catalyzed ATRP is provided. Contributions of involved species are examined mechanistically, followed by challenges and future directions towards the next generation of advanced functional macromolecular materials.

Tunable physicochemical properties combined with the high chemical and thermal stabilities of covalent organic frameworks (COFs) make them ideal candidates for the next generation of energy storage systems. The integration of redox-active moieties (e.g., thiols) in COFs imparts them a pseudocapacitive characteristic and represents an efficient strategy to boost their performance as electrochemical supercapacitors (SCs). We report the synthesis of two thiol-decorated COFs (SH-COF-1 and SH-COF-2) via the condensation between 2,5-diaminobenzene-1,4-dithiol (DABDT) and benzene-1,3,5-tricarboxaldehyde (TBA), or 1,2,4,5-tetrakis-(4-formylphenyl)benzene (TFPB), respectively. SH-COF-1, which possesses a higher number of thiol groups per structural repeat unit compared to SH-COF-2, exhibits a higher surface area (227 m² g⁻¹) and enhanced electrochemical performance (areal capacitance of 118 mF cm⁻² and a capacitance retention >95% after 1000 cycles), being superior to previously reported COFs missing redox-active units in their scaffolds. Moreover, to demonstrate the multifunctionality resulting from the presence of thiol groups, AuNPs were in situ grown using SH-COFs as templates. By taking advantage of the strength of the bonding between the AuNPs and the SH-COFs, Au-SH-COF hybrids were used as heterogeneous catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), showing an excellent catalytic activity k_obs, of 1.01 min⁻¹ and 0.71 min⁻¹ for Au-SH-COF-1 and Au-SH-COF-2, respectively, and long-term performance (4-NP to 4-AP conversion above 95% after 10 catalytic cycles). This work highlights the importance of COFs' molecular design towards the development of highly efficient (multi)functional materials.

Lanthanides have relatively recently been recognized as ideal candidates for the construction of advanced magnetic materials that would allow for their future applications in spintronics and high-density data storage. Despite enormous progress that deals with the control of magnetic anisotropy and slow relaxation of magnetization in Single Molecule Magnets (SMMs), further improvements are still indispensable to go beyond the ultra-low temperature regime. We have thus prepared four lanthanide complexes ([ErL₂(OTf)(MeOH)₂](OTf)₂ (1), [YbL₂(OTf)₂](OTf) (2), [ErL(NO₃)₃(H₂O)](3) and [YbL(NO₃)₃(MeOH)]·MeCN (4)) with a tridentate Schiff-base ligand L, to unravel magneto-structural correlations in this new family of field-induced Single Ion Magnets (SIMs). Interestingly, as revealed by the single crystal X-ray diffraction, their structures are synthetically tuned by the choice of the applied counterion. The static and dynamic magnetic properties of 1–4 were investigated revealing that all compounds behave as field-induced Single Ion Magnets (SIMs). Their energy barriers U_eff decrease in the sequence: 4, 2, 3, 1, with an order of magnitude difference between the highest and the lowest value. To correlate the observed magnetic properties with spectroscopic data, low-temperature absorption spectroscopy was performed. This has allowed the determination of the energy levels of the Ln(III) ions and the exact composition of the state vectors for the Ln(III) ground multiplets via crystal-field analysis (CFA) and semiempirical superposition model (SPM) approach. Theoretical and magneto-structural correlation studies indicate that one can modulate the heterotopic coordination spheres around the prolate Er(III) and Yb(III) solely with the counterions. This leads to rarely observed high-coordinate SIM species with the LnN_xO_y first coordination sphere (where Ln – Er or Yb, x = 3 or 6, y = 2, 3 or 6). Their performance can be related to the intricate interactions between the electron density on the Ln ion and the crystal field created by the surroundings.