Dalton Transactions

doi: 10.1039/d5dt90073epmid: N/A

doi: 10.1039/d5dt90074cpmid: N/A

Eusamio, Javier; Grabulosa, Arnald

doi: 10.1039/d4dt03572kpmid: 39960367

The synthesis, complexation and main catalytic applications in enantioselective homogeneous catalysis of enantiopure single-atom-bridged diphosphorus ligands ((R1R2)P–X–P(R3R4); X = CR2, NR, O) is reviewed, covering the literature up to the beginning of 2025. The information is organised by ligand type, with unsubstituted methylene-bridged (–CH2–) and substituted amino-bridged (–NR–) diphosphorus ligands being by far the most common type of ligands. The perspective review is completed by the analysis of all reported crystal structures of bidentate monometallic complexes with the ligands. The bite angles, metal–phosphorus distances and buried volumes (Vbur) are given in the ESI.

Martin, Lee; Wallis, John D.; Ogar, Joseph O.

doi: 10.1039/d5dt00249dpmid: 40071889

There has been growing interest in recent years in the synthesis of multifunctional materials that exhibit both chirality and electrical conductivity. These materials can exhibit electrical magnetochiral anisotropy (eMChA) or the chirality induced spin selectivity (CISS) effect. Several families of chiral tetrathiafulvalene (TTF)-based donor molecules have been successfully used with acceptors or simple anions to prepare chiral molecular conductors. Chiral materials have also been obtained by employing racemic or enantiopure counter anions with chiral or achiral TTF donors. Most recently, enantiopure molecular conductors of bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and 2,5-bis(1,3-dithiolan-2-ylidene)-1,3,4,6-tetrathiapentalene (BDH-TTP) have been obtained through chiral induction from a racemic mixture of a coordination complex, which provides the anion. This Frontier article provides an overview of chiral molecular conductors and a summary of progress to date. It highlights future perspectives on how chirality can be introduced into molecular conductors by employing enantiopure or racemic coordination complexes, which also have the potential to introduce magnetism into the multifunctional material.

Huang, Huilin; Yang, Qiong; Yao, Kun; Geng, Wenchao; Jing, Xu

doi: 10.1039/d5dt00120jpmid: 40126519

We have designed and synthesized an aesthetically appealing two-dimensional copper-cluster-based organic framework material named Cu-BPYC. This material exhibits superior charge separation and transfer efficiency, as well as reactive oxygen species (ROS) generation capability under visible-light irradiation. Through the synergistic mechanisms of photo-induced energy and charge transfer, it effectively promotes the oxidation of amines to imines. Additionally, Cu-BPYC demonstrates excellent structural stability and reusability in heterogeneous catalytic systems.

Volkov, Sergey; Yang, Xia; Kireev, Vadim; Banaru, Alexander; Han, Shujuan; Gosteva, Alevtina; Arsent'ev, Maxim; Charkin, Dmitri; Povolotskiy, Alexey; Savchenko, Yevgeny; Krzhizhanovskaya, Maria; Vorobiev, Stepan; Vaitieva, Yulia; Aksenov, Sergey; Zhang, Fangfang

Claude, Guilhem; Ellwanger, Mathias A.; Grippo, Adam; Hernandez, Ritchie; Figueroa, Joshua R.; Abram, Ulrich

doi: 10.1039/d5dt00634apmid: 40143757

A stepwise ligand exchange starting from [Mn(CO)5Br] allows the synthesis of the heteroleptic isocyanide manganese(i) complex mer,trans-[Mn(CNp-FArDArF2)3(CNtBu)2Br] (DArF = 3,5-(CF3)2C6H3, tBu = tert-butyl). Subsequent reduction gave the first heteroleptic isocyanide manganese(−1) complex, [K(18-crown-6)][Mn(CNp-FArDArF2)3(CNtBu)2], exhibiting a five-coordinate, trigonal bipyramidal coordination sphere.

Dong, Qing-Shu; Wang, Ning; Young, David James; Hu, Fei-Long; Mi, Yan

doi: 10.1039/d5dt00208gpmid: 40152709

Three structurally related cadmium coordination polymers CP1–CP3 {[Cd3(Pebpeb)2(L1)6] (CP1), [Cd3(Pebpeb)2(L2)6] (CP2) and [Cd6(Pebpeb)4(L3)12]·HL3 (CP3)} were constructed from the photoactive alkene ligand Pebpeb (Pebpeb = 4,4′-((1E,1′E)-(5-(pyridin-3-ylethynyl)-1,3-phenylene)bis(ethene-2,1-diyl))dipyridine; HL1 = 3-chlorobenzoic acid; HL2 = 3-nitrobenzoic acid; HL3 = 3-isopropyl benzoic acid) and Cd(ii) ions in the presence of different auxiliary carboxylic acids. Different conformations of the functional olefinic ligand Pebpeb were observed in CP1–CP3 despite their similar 1D chain motif. [2 + 2] Solid-state photodimerization occurred when crystals of CP1–CP3 were irradiated with UV light (365 nm) and each displayed different photosalient (PS) responses attributed to the different bulkiness of the auxiliary carboxylic acids employed. A simple photoactuating device was prepared using a CP1-PVA (PVA = Polyvinyl Alcohol) composite.

Seki, Kota; Nakamura, Takashi

doi: 10.1039/d5dt00623fpmid: 40159943

Selective complexation of specific units in homooligomers is usually challenging due to their similar reactivity. We now report a heteronuclear complex using a macrocyclic ligand with four identical ONO chelating units, which was synthesized by selective coordination to molybdenum at two diagonal units, followed by palladium at the remaining units.

Murphy, Fáinché; Kennedy, Alan R.; Weetman, Catherine E.

doi: 10.1039/d5dt00379bpmid: 40163545

Understanding and controlling facile reduction chemistry is a key challenge in molecular main group chemistry. Herein, we report the divergent reduction chemistry of aluminium(iii) hydrides supported by N-heterocyclic carbenes (NHCs). Choice of reducing agent and NHC ligand are key, with Al(ii) dialanes, Al(ii) cations, asymmetric Al(ii) dialanes and ligand exchange reactions all identified via NMR and single crystal X-ray diffraction.