Dalton Transactions

doi: 10.1039/d5dt90109jpmid: N/A

doi: 10.1039/d5dt90110cpmid: N/A

Kundu, Gargi; Sen, Sakya S.

doi: 10.1039/d5dt00648apmid: 40259828

In recent years, there has been a remarkable surge in the utilization of saturated N-heterocyclic carbenes (NHCs) as ligands in main group chemistry. While the field has predominantly focused on five-membered NHCs and cyclic alkyl(amino) carbene (CAAC) ligands, the investigation of six-membered NHCs (6-NHCs) has only just begun. Despite possessing higher nucleophilicity than their five-membered counterparts, 6-NHCs have been less explored due to their lack of structural rigidity. This feature article aims to highlight recent developments in 6-NHCs in only main group chemistry. Exciting new studies have demonstrated the activation of B–H bonds in HBpin, ring expansion from a six-membered to a seven-membered ring under ambient conditions, and the stabilization of transient units “H–B00000000000000000000000000000000111111110000000011111111000000000000000000000000O” and “(OH)BO”, among other intriguing phenomena. A major focus of this review is on synthetic approaches for 6-NHC-stabilized main-group compounds and their unusual properties, as revealed by spectroscopic and crystallographic data. While the chemistry of 6-NHCs is still in its nascent stage, the findings presented in this feature article underscore the need for its exploration and further investigation. Furthermore, this review provides valuable insights into effective synthetic methods for creating new 6-NHC·main group (B, Al, Si, P, Zn, etc.) complexes, along with mechanistic explanations for some of these reactions. These advances hold great promise for the future development of this exciting and rapidly evolving field of N-heterocyclic carbene chemistry.

Marschner, Christoph

doi: 10.1039/d5dt00956apmid: 40455492

The last few years have witnessed exciting development in the chemistry of silylated rare earths and heavier f-elements. First examples of silylated lanthanum (La) and praseodymium (Pr) complexes have been reported so that currently out of all lanthanides only for the radioactive promethium (Pm) silylated complexes are unknown. Previously unknown U(iii) silyl complexes have also been described. Spectacular examples of the elusive trisilylated complexes of lanthanides and actinides have been presented. These show unusual magnetic properties, making them susceptible to facile 29Si NMR spectroscopic characterization, which could be rather difficult for compounds with diminished silylation degree. Novel silylene complexes were shown to catalyze hydrosilylation reactions. The novel compound class of silole coordinated f-element complexes was introduced by La and erbium (Er) complexes with the latter exhibiting single molecule magnetic properties.

Lin, Peng; Yang, Junpu; Sun, Weinan; Zhou, Xiaoyuan; Zhao, Fangbo; Lin, Jian

doi: 10.1039/d5dt00965kpmid: 40407787

We report the first study of a bismuth-based metal–organic framework as a scintillator for X-ray detection and imaging. The newly synthesized Bi-TCPE exhibits strong photoluminescence and efficient X-ray-induced radioluminescence, along with excellent stability. Its integration into a flexible polymer matrix enables X-ray imaging, highlighting the great promise of Bi-MOFs as a new class of low-toxicity scintillators.

Zacher, Peter A.; Unruh, Daniel K.; Daly, Scott R.

doi: 10.1039/d5dt01076dpmid: 40433924

Here we describe the first coordination complexes containing a bulky m-terphenyltrihydroborate ligand. Treating [UI3(thf)4] and NdCl3 with three equiv. of Li(H3BArtBu4)(Et2O) (where ArtBu4 = 2,6-(3,5-tBu2C6H3)2C6H3) yielded [M(H3BArtBu4)3(thf)2] (M = U and Nd). [U(H3BArtBu4)3(dme)2] is also described, and structural comparisons reveal the influence of the Lewis base on H3BArtBu4 positioning.

Kinoshita, Kana; Yang, Yiming; Nagano, Shiho; Horiuchi, Shinnosuke; Nakao, Yoshihide; Omoto, Kenichiro; Sakuda, Eri; Arikawa, Yasuhiro; Umakoshi, Keisuke

doi: 10.1039/d5dt01078kpmid: 40434796

Herein, we report novel square-planar Pd(ii) complexes bearing two Ag2(Ar2pz)3 units as self-assembled trans-chelating ligands. This structural motif is unique to Pd(ii) ions and cannot be obtained from a Pt(ii) metal source owing to the stronger dative bonding nature of the Pt(ii) ion compared to that of the Pd(ii) ion.

Khan, Yaqoot; Du, Yunyun; Yan, Li; Zhang, Niu; Zhang, Menglei; Ma, Hongwei; Li, Hui

doi: 10.1039/d5dt00786kpmid: 40421485

Understanding the coordination geometry of nucleotide mono-, di-, and triphosphates is pivotal for unraveling the intricate relationships between molecular structure and biological function, particularly in metal–ligand interactions and their role in biomolecular recognition. This study investigates the structure of nucleotide–metal polymers and their selective interactions with amino acids, specifically tryptophan (Trp) and tyrosine (Tyr). We synthesized and comprehensively analyzed five coordination polymers of cytidine nucleotides: cytidine monophosphate (CMP), deoxycytidine monophosphate (dCMP), cytidine diphosphate (CDP), and cytidine triphosphate (CTP), which are {[Cu(CMP)(bpa)(H2O)3](CMP)·3H2O}n (1), {[Cu2(dCMP)(4,4′-bipy)2(H2O)2]·4H2O}n (2), {[Cu2(CDP)2(azpy)(H2O)]·3H2O}n (3), {[Cd2(CDP)2(bpa)2(H2O)2]·8H2O}n (4), and {[Cu(CTP)(2,2′-bipy)]·2H2O}n (5), where (3), (4) and (5) mark the first report of CDP and CTP coordination complexes. Single-crystal X-ray diffraction unveiled the structure of the polymers to be one-dimensional (1, 5) or two-dimensional (2, 3, 4). Circular dichroism (CD) spectroscopy in both the solid and solution states elucidates the chirality-driven assembly in these nucleotide–metal polymers. The selective interactions of coordination polymers with tryptophan (Trp) and tyrosine (Tyr) were studied using spectroscopic titrations. Experimental and computational analyses reveal distinct interactions between all five coordination polymers and the amino acids, highlighting their biosensing potential. Binding affinity variations across the polymers offer insights into nucleotide–metal coordination chemistry and suggest applications in molecular recognition and functional materials.

Ye, Jiansheng; Dai, Yali; Liu, Wenjun; Xu, Jingrou; Li, Jialing; Chen, Meng; Yang, Sha; Li, Qinzhen; Du, Yuanxin; Chai, Jinsong; Zhu, Manzhou

doi: 10.1039/d5dt00604jpmid: 40384284

Zhang, Xuan; Wang, Xueling; Ta, Hongbo; Liu, Zhiliang

doi: 10.1039/d5dt00780apmid: 40384361

The preparation of high-efficiency electromagnetic wave (EMW) absorption materials usually requires the matching of dielectric and magnetic components. However, simultaneously tuning the dielectric and magnetic properties of materials still faces a significant challenge. Herein, a series of metal/carbon-based CeO2/Fe3C/CNT (CF-CNT-x, x = 1, 2, 3) composites derived from Ce-based Prussian blue analogues (Ce[Fe(CN)6]·5H2O, CeFe-PBA) with different morphologies via adjusting the solvent environment was prepared. The composites not only inherit the morphology of the CeFe-PBA precursors but also generate a large number of carbon nanotubes (CNTs), further tuning the balance of dielectric and magnetic components. Due to the highest anisotropy bipyramidal morphology, multi-polarization mechanisms, and magnetic–dielectric synergies, the obtained CF-CNT-2 exhibits excellent EMW absorption performance with a filling ratio of merely 20 wt%, a minimum reflection loss (RLmin) of −62.60 dB and an effective absorption bandwidth (EAB) of 5.28 GHz at 2.00 mm. Meanwhile, CST simulations show that the maximum radar cross-section reduction of CF-CNT-2 reaches 31.63 dB m2, confirming its great practical application potential. This work effectively elucidates the mechanism of the influence of the morphology of PBA-based EMW absorption materials on the dielectric and magnetic properties, and confirms the great potential of rare earth (RE)-based PBA derivatives as EMW absorption materials.