Dalton Transactions

Oloyede, Ugochinyere N.; Flowers, Robert A.

doi: 10.1039/d3dt03454bpmid: 38224159

Bond activation of small molecules through coordination to low valent metal complexes in M⋯X–H type interactions (where X = O, N, B, Si, etc.) leads to the formation of unusually weak X–H bonds and provides a powerful approach for the synthesis of target compounds under very mild conditions. Coordination of small molecules like water, amides, silanes, boranes, and dinitrogen to Ti(iii) or Ti(ii) complexes results in the synergetic redistribution of electrons between the metal orbitals and the ligand orbitals which weakens and enables the facile cleavage of the X–H or N–N bonds of the ligands. This review presents an overview of coordination-induced bond activation of small molecules by low valent titanium complexes. In particular, the applications of low valent titanium-induced bond weakening in nitrogen fixation are presented. The review concludes with potential future directions for work in this area including low-valent Ti-based PCET systems, photocatalytic nitrogen reduction, and approaches to tailoring complexes for optimal bond activation.

Yao, Haiyu; Wang, Peijie; Zhu, Min; Shi, Xue-Rong

doi: 10.1039/d3dt03820cpmid: 38229516

Exploring efficient and low-cost oxygen evolution reaction (OER) electrocatalysts reaching the industrial level current density is crucial for hydrogen production via water electrolysis. In this feature article, we summarize the recent progress in hierarchical nanostructures for the industrial-level OER. The contents mainly concern (i) the design of a hierarchical structure; (ii) a Ni-based hierarchical structure for the industrial current density OER; and (iii) the surface reconstruction of the hierarchical structure during the OER process. The work provides valuable guidance and insights for the manufacture of hierarchical nanomaterials and devices for industrial applications.

Romo-Islas, Guillermo; Gil-Moles, María; Saxena, Arnav; Frontera, Antonio; Gimeno, M. Concepción; Rodríguez, Laura

doi: 10.1039/d3dt04050jpmid: 38174938

Twelve (N^N^N)platinum pyridyl complexes, (N^N^N)Pt(pyF), were synthesised and investigated for their singlet oxygen generation and potential biological activities. They exhibited 1IL and 1MLCT absorption transitions at approximately 325 and 360 nm, identified through TD-DFT calculations. Luminescence was observed only in the L1-derived compounds in solution, with a dual emission with the main contribution of phosphorescence under deaerated conditions. Room temperature phosphorescence was detected in all solid-state cases. Electron-withdrawing substituents at specific positions (R1 and X) and the number of fluorine atoms in R2 were found to enhance the photosensitizing capabilities of these compounds. Biological assessments, including cytotoxicity and photocytotoxicity, were conducted to evaluate their potential as chemotherapeutic agents and photosensitizers. Complexes with chloro substitution in the N^N^N tridentate ligand of the central pyridine ring exhibited promising chemotherapeutic properties. Ancillary pyridine ring substitution became significant under irradiation conditions, with fluoromethylated substituents enhancing cytotoxicity. Complex 2-CF3 was the most efficient singlet oxygen producer and a highly effective photosensitizer. CHF2-substituted complexes also showed improved photosensitizing activity. DNA binding studies indicated moderate interactions with DNA, offering insights into potential biological applications.

Panja, Anangamohan; Paul, Sagar; Moreno-Pineda, Eufemio; Herchel, Radovan; Jana, Narayan Ch.; Brandão, Paula; Novitchi, Ghenadie; Wernsdorfer, Wolfgang

doi: 10.1039/d3dt03557cpmid: 38205580

In the last two decades, efforts have been devoted to obtaining insight into the magnetic interactions between CuII and LnIII utilizing experimental and theoretical means. Experimentally, it has been observed that the exchange coupling (J) in CuII–LnIII systems is often found to be ferromagnetic for ≥4f7 metal ions. However, exchange interactions at sub-Kelvin temperatures between CuII and the anisotropic/isotropic LnIII ions are not often explored. In this report, we have synthesized a series of heterobimetallic [CuLn(HL)(μ-piv)(piv)2] complexes (LnIII = Gd (1), Tb (2), Dy (3) and Er (4)) from a new compartmental Schiff base ligand, N,N’-bis(3-methoxy-5-methylsalicylidene)-1,3-diamino-2-propanol (H3L). X-ray crystallographic analysis reveals that all four complexes are isostructural and isomorphous. Magnetic susceptibility measurements reveal a ferromagnetic coupling between the CuII ion and its respective LnIII ion for all the complexes, as often observed. Moreover, μ-SQUID studies, at sub-Kelvin temperatures, show S-shaped hysteresis loops indicating the presence of antiferromagnetic coupling in complexes 1–3. The antiferromagnetic interaction is explained by considering the shortest Cu⋯Cu distance in the crystal structure. The nearly closed loops for 1–3 highlight their fast relaxation characteristics, while the opened loops for 4 might arise from intermolecular ordering. CASSCF calculations allow the quantitative assessment of the interactions, which are further supported by BS-DFT calculations.

Zhang, Yuhong; Cai, Wentong; Liu, Jian; Zhang, Ziyi; Sun, Bo; Liu, Hang

doi: 10.1039/d3dt03331gpmid: 38221878

Herein, a series of Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) phosphors is prepared via a solid-state reaction. The upconversion and downshift luminescence properties of the phosphors were investigated under an excitation of 980 nm. The bright blue light emission from Tm3+ ion and the green and red light emissions from Ho3+(Er3+) ions were observed. The near-infrared light intensity of NIR-I (Tm3+, ∼850 nm), NIR-II (Er3+: ∼1550 nm; Tm3+: ∼1783 nm) and NIR-III (Ho3+: ∼2050 nm) were analyzed. In particular, the dramatic thermal enhancement phenomenon in visible and NIR regions was exhibited by the Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) phosphors. Among them, the green light intensity of Er3+ ions increased 26.77 times, from 303 to 573 K. The NIR-II emission band (∼1783 nm) intensity of Tm3+ ions at 533 K increased 168.7 times compared to that at 313 K. The possible thermal enhancement mechanism is illustrated by the negative thermal expansion (NTE) and Frenkel defect of the Y2W3O12 host. Finally, the optical temperature sensing performances of Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) samples are investigated according to the luminescence intensity dependence relationship on temperature. The maximum value of SR reached 4.24% K−1 at 353 K for Y2W3O12:10%Yb3+/0.6%Ho3+ phosphor. The results indicate that the Y2W3O12:10%Yb3+/x%RE3+ (RE = Er/Ho/Tm) phosphors possess anti-thermal quenching properties and are suitable for developing optical temperature sensors.

Muneeswaran, Zilma Pereira; Teoman, Baran; Wang, Yu; Chaudhry, Haroon; Brinzari, Tatiana V.; Verma, Gaurav; Ranasinghe, Lomaani; Kaler, Kylie Ryan; Huang, Xiaoyi; He, Xing; Thomas, Belvin; Xu, Shiyou; Cheng, Chi-Yuan; Boyd, Jeffrey M.; Chen, Dailin;

Fateev, Sergey A.; Kozhevnikova, Vladislava Y.; Kuznetsov, Kirill M.; Belikova, Daria E.; Khrustalev, Victor N.; Goodilin, Eugene A.; Tarasov, Alexey B.

doi: 10.1039/d3dt03452fpmid: 38226672

In recent years, hybrid manganese(ii) halides (HMHs) have attracted wide attention due to their impressive optical properties, low toxicity, and facile synthetic processibility. Being effective reabsorption-free phosphors, these compounds demonstrate the potential to be used as low-cost solution-processable scintillators. However, most of the HMHs studied to date contain bulk organic cations and, as a result, are characterized by low density and low X-ray stopping power. For this reason, we studied manganese(ii) bromides with compact organic cations such as formamidinium (FA+) and acetamidinium (AcA+). In particular, we synthesized four new phases, two of which are characterized by octahedral coordination of manganese ions ((FA)MnBr3 and (AcA)MnBr3) and red emission, whereas the other two have tetrahedrally coordinated Mn2+ ions ((FA)3MnBr5 and (AcA)2MnBr4) and green emission. Photoluminescence (PL) and radioluminescence measurements demonstrated high PL quantum yields and reasonable scintillation light yields of acetamidinium-based compounds. In addition, unlike most known HMH-based scintillators, the discovered materials have a relatively high density due to the small fraction of the volume occupied by organic cations, so their X-ray attenuation coefficients are comparable to the well-known oxide scintillators.

Li, Heng; Wang, Ke; Yang, Lin; Luo, Yu-Zhou; Yao, Zi-Jian

doi: 10.1039/d3dt04078jpmid: 38226891

Novel half-sandwich ruthenium complexes termed [(p-cymene)RuClL] were synthesized by chelating arylhydrazone ligands with [(p-cymene)RuCl2]2 and were then fully characterized using different spectroscopic and analytical techniques. The crystal structure of complex 4 indicated that the hydrazone ligands bonded to the ruthenium ion in a bidentate manner through the imine nitrogen and imidazolate oxygen, exhibiting a pseudo-octahedral geometry centered by the ruthenium atom. The as-fabricated air and moisture stable half-sandwich ruthenium complexes demonstrated excellent catalytic activity towards the N-alkylation of hydrazides under mild conditions. Under the catalysis of ruthenium complexes, acyl hydrazides were reacted with different types of alcohols in a one-pot reaction, resulting in N-alkylation hydrazides with different substituents. This catalyst exhibited characteristics such as high catalytic efficiency, broad substrate scope, and mild reaction conditions, indicating that it has great potential for industrial applications.