Dalton Transactions

doi: 10.1039/d3dt90160bpmid: N/A

doi: 10.1039/d3dt90161kpmid: N/A

doi: 10.1039/d3dt90162apmid: N/A

Li, Jikun; Wei, Chuanping; Han, Yinfeng; Hu, Changwen

doi: 10.1039/d3dt02249hpmid: 37646095

Polyoxovanadates (POVs) have received widespread attention in catalytic applications due to their various structures and remarkable redox properties. By introducing a second transition metal, POV-based inorganic–organic hybrid (POVH) catalysts show increasing stability and more catalytic active sites compared with pure POVs. In this perspective article, POVH materials as oxidative catalysts have been classified into two main categories according to the interactions between transition metal-complex units and POV clusters: (i) hybrids with metal–organic units act as isolated cations and (ii) hybrids with an organic ligand coordinate to the second transition metal, which is further linked to a POV cluster via oxygen bridges directly or indirectly to give zero-, one-, two- or three-dimensional supramolecular structures. The oxidative conversion of organic compounds, including thiophene derivatives, thioethers, alkanes, alcohols, and alkenes, and oxidative detoxification of a sulfur mustard simulant or degradation of lignin, along with the oxidative photo/electrocatalytic transformation of organic compounds catalyzed by POVH materials, are discussed in detail. Furthermore, the challenges and prospects toward the development of POVH catalysts are explored briefly from our perspectives.

Hyvl, Jakub

doi: 10.1039/d3dt02313cpmid: 37670510

Hypervalent (three-center, four-electron) bonding in organobismuth complexes has been extensively studied due to its ability to affect molecular geometry, dynamic behavior, or to stabilize the ligand scaffold. This work addresses the effects of this bonding on reactivity, catalytic activity, redox processes, and its potential applications in biosciences, materials science, and small molecule activation.

Sunkari, Sailaja S.; Verma, Abhineet; Pandey, Om; Gupta, Shraddha; Wakizaka, Masanori; Takaishi, Shinya; Kawasoko, Hideyuki; Fukumura, Tomoteru; Yamashita, Masahiro

doi: 10.1039/d3dt02244gpmid: 37614169

The first slow magnetic relaxation in a ferromagnetic Cu(ii) chain compound, Cu(dipic)(OH2)2 (dipicH2 = pyridine-2,6-dicarboxylic acid), induced by a phonon bottleneck effect under a magnetic field of 0.6 T, with a relaxation time of 2.2 s at 2.8 K, was observed.

Das, Utpal; Paira, Priyankar

doi: 10.1039/d3dt01348kpmid: 37314097

The phototoxic nature of drugs has been seen to convey immense importance in photo activated chemotherapy (PACT) for the selective treatment of disease. Rationally, in order to eradicate the vehemence of cancer in a living body, the design of phototoxic molecules has been of growing interest in research to establish a selective strategy for cancer therapy. Therefore, the present work portrays the synthesis of a phototoxic anticancer agent by incorporating ruthenium(ii) and iridium(iii) metals into a biologically active 2,2′-biquinoline moiety, BQ. The complexes, RuBQ and IrBQ, have been revealed as effective anticancer agents with remarkable toxicity in the presence of light compared to the dark towards HeLa and MCF-7 cancer cell lines due to the production of a profuse amount of singlet oxygen (1O2) upon irradiation by visible light (400–700 nm). Complex IrBQ exhibited the best toxicity (IC50 = 8.75 μM in MCF-7 and 7.23 μM in HeLa) in comparison to the RuBQ complex under visible light. RuBQ and IrBQ displayed considerable quantum yields (Φf) along with a good lipophilic property, indicating the cellular imaging capability of both complexes upon significant accumulation in cancer cells. Also, the complexes have shown significant binding propensity with biomolecules, viz. deoxyribonucleic acid (DNA) as well as serum albumin (BSA, HSA).

Naina, Vanitha R.; Singh, Akhil K.; Shubham, ; Krätschmer, Frederic; Lebedkin, Sergei; Kappes, Manfred M.; Roesky, Peter W.

doi: 10.1039/d3dt02317fpmid: 37642577

The synthesis of heteroleptic Cu(i) complexes with coumarin-functionalized aminodiphosphine and diimine ligands is described. The complexes show yellow to deep-red phosphorescence in the solid state at ambient temperature with quantum yields up to 21%. The emission color of the complexes can be tuned by systematic modifications in the ligand system.

Vrána, Jan; Růžičková, Zdeňka; Růžička, Aleš; Dostál, Libor

doi: 10.1039/d3dt01859hpmid: 37610275

In this study, we report a group of alkali metal aluminates bearing bis(organoamido)phosphane ligand. The starting complex {[PhP(NtBu)2]AlMe2}Li·OEt2 (1) was prepared by stepwise deprotonation of the parent PhP(NHtBu)2 by nBuLi and AlMe3. Further derivatization of aluminate 1 was performed by the virtual substitution of lithium -{[PhP(NtBu)2]AlMe2}K (2), methyl substituents – {[PhP(NtBu)2]AlH2}Li·THF (3), modification of steric bulk and induction effects on the phosphorus atom – {[tBuP(N-2,6-iPr2C6H3)2]AlMe2}Li·(OEt2)2 (4), and phosphorus atom oxidation state {[Ph(Y)P(NtBu)2]AlMe2}Li (Y = O (5), S (6), Se (7), Te (8)). The structure causing non-covalent interactions in 1–4 were evaluated with the help of theoretical calculations and topological analysis ranging from π-electron system-metal to agostic interactions of various types. The further reactions of 1 with various nucleophiles were found to be a versatile tool for the preparation of iminophosphonamides via the formation of P–E bond (E = Si, Ge, Sn, Pb, P, and C) and followed by P(iii) → P(v) tautomeric shift.

Yao, Zhiqian; Xu, Suqiong; Zhang, Xianke; Zhu, Jiawei; Liao, Peng; Yuan, Jujun; Rong, Chuicai; Liu, Xiaoqing; Xiong, Zuzhou; Kang, Shuying; Kuang, Fangguang

doi: 10.1039/d3dt02036cpmid: 37615584