Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102653
Shaozhi Du , Fanshu Cao , Xuyang Wang , Binglin Lei , Zhenbo Mo
Diatomic molecules composed of group 14 elements are of significant interest because they present opportunities for exploring new frontiers in chemical bonding, reactivity, and materials design. Typically, these molecules are highly unstable and are primarily observed in the gas phase. To date, heterodiatomic molecules of group 14 elements have not been successfully isolated in condensed phases despite their importance in materials science and electronics. In this study, we successfully synthesized a heterodiatomic silicon-germanium (SiGe) molecule, characterized by a Si=Ge double bond and two lone pairs of electrons located on the Si and Ge atoms, by using an N-heterocyclic imino-substituted silylene. The SiGe molecule undergoes versatile chemical transformations, including transferring the Si(0) or Ge(0) fragments, deprotonating the C–H bond in N-tosylimine, and reacting with acrylonitrile, to construct valuable SiGe-containing compounds. This research provides critical insights into the electronic structure and reactivity of heterodiatomic main-group complexes.
{"title":"A silylene-stabilized heterodiatomic SiGe molecule","authors":"Shaozhi Du , Fanshu Cao , Xuyang Wang , Binglin Lei , Zhenbo Mo","doi":"10.1016/j.chempr.2025.102653","DOIUrl":"10.1016/j.chempr.2025.102653","url":null,"abstract":"<div><div>Diatomic molecules composed of group 14 elements are of significant interest because they present opportunities for exploring new frontiers in chemical bonding, reactivity, and materials design. Typically, these molecules are highly unstable and are primarily observed in the gas phase. To date, heterodiatomic molecules of group 14 elements have not been successfully isolated in condensed phases despite their importance in materials science and electronics. In this study, we successfully synthesized a heterodiatomic silicon-germanium (SiGe) molecule, characterized by a Si=Ge double bond and two lone pairs of electrons located on the Si and Ge atoms, by using an N-heterocyclic imino-substituted silylene. The SiGe molecule undergoes versatile chemical transformations, including transferring the Si(0) or Ge(0) fragments, deprotonating the C–H bond in N-tosylimine, and reacting with acrylonitrile, to construct valuable SiGe-containing compounds. This research provides critical insights into the electronic structure and reactivity of heterodiatomic main-group complexes.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102653"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144578129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102656
Dongsheng Mao , Hongquan Gou , Wen Chen , Rui Zhu , Fanping Zhang , Wentao Zhang , Yuanyuan Zhang , Xiaozhi Huang , Min Li , Wenxing Li , Bing Shen , Xiaoli Zhu
Orthogonal detection of multiple targets is essential for precision medicine, but achieving this in homogeneous systems is challenging owing to coordination issues regarding reagents and detection platforms. Here, we developed an enzymatic DNA orthogonal chemistry-based 3D spectral fingerprint (EzDo-CRAFT) platform, which integrates nicking endonuclease-based orthogonality with excitation-emission matrix (EEM) spectroscopy-based 3D signal resolution. Notably, we discovered that the nicking endonuclease Nt.BstNBI exhibits sensitivity to variable recognition sites and that their reaction processes are highly orthogonal, which laid the foundation for EzDo-CRAFT. Moreover, EEM spectroscopy effectively overcomes the limitations of spectral overlap and provides 3D spectral fingerprint features with high information density. The EzDo-CRAFT platform enabled one-pot detection of 10 targets across bladder cancer, prostate cancer, kidney cancer, and healthy individuals, using clinical urine samples, demonstrating high sensitivity (82.7%, 95% CI: 63.5%–93.5%) and specificity (81.8%, 95% CI: 47.8%–96.8%). This EzDo-CRAFT platform demonstrates an innovative application of nicking endonucleases and their potential for advancing precision medicine.
{"title":"Enzymatic DNA orthogonal chemistry for multi-cancer diagnosis","authors":"Dongsheng Mao , Hongquan Gou , Wen Chen , Rui Zhu , Fanping Zhang , Wentao Zhang , Yuanyuan Zhang , Xiaozhi Huang , Min Li , Wenxing Li , Bing Shen , Xiaoli Zhu","doi":"10.1016/j.chempr.2025.102656","DOIUrl":"10.1016/j.chempr.2025.102656","url":null,"abstract":"<div><div>Orthogonal detection of multiple targets is essential for precision medicine, but achieving this in homogeneous systems is challenging owing to coordination issues regarding reagents and detection platforms. Here, we developed an enzymatic DNA orthogonal chemistry-based 3D spectral fingerprint (EzDo-CRAFT) platform, which integrates nicking endonuclease-based orthogonality with excitation-emission matrix (EEM) spectroscopy-based 3D signal resolution. Notably, we discovered that the nicking endonuclease Nt.BstNBI exhibits sensitivity to variable recognition sites and that their reaction processes are highly orthogonal, which laid the foundation for EzDo-CRAFT. Moreover, EEM spectroscopy effectively overcomes the limitations of spectral overlap and provides 3D spectral fingerprint features with high information density. The EzDo-CRAFT platform enabled one-pot detection of 10 targets across bladder cancer, prostate cancer, kidney cancer, and healthy individuals, using clinical urine samples, demonstrating high sensitivity (82.7%, 95% CI: 63.5%–93.5%) and specificity (81.8%, 95% CI: 47.8%–96.8%). This EzDo-CRAFT platform demonstrates an innovative application of nicking endonucleases and their potential for advancing precision medicine.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102656"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The missing BN isostere of coronene, 2a1,6a1,10b1-triaza-2b,6b,10b-triborahexabenzo[a,d,g,j,m,p]coronene, was synthesized in a one-shot procedure from 2,4,6-tribenzhydryl-1,3,5-triazine via a dearomative triple borylation. In the crystalline state, the resulting nearly D3-symmetric molecule forms an efficient 3D π-stacking network, with disorder observed in the B–N and C=C bonds. Density functional theory (DFT) calculations of electronic couplings predict a promising potential for applications in organic semiconducting materials. The introduction of six additional methyl groups suppressed this disorder, enabling precise bond-length alternation analysis. Notably, the incorporation of three BN units into the spoke positions of the coronene core induced a paratropic ring current in the N3C3 central ring, a hypsochromic shift in absorption and emission maxima, and an enhanced photoluminescence quantum yield. Furthermore, selective single and double borylations of 2,4,6-tribenzhydryl-1,3,5-triazine were demonstrated, alongside a dearomative triple borylation of its benzothiophene analog. These findings may accelerate advances in both fundamental and applied chemistry based on BN/CC isosterism.
{"title":"One-shot synthesis of BN-embedded hexabenzocoronene via a dearomative triple borylation","authors":"Soichiro Nakatsuka , Takehiro Yamamoto , Hiroaki Abe , Shione Kiriyama , Masashi Mamada , Nobuhiro Yasuda , Susumu Oda , Chihaya Adachi , Takuji Hatakeyama","doi":"10.1016/j.chempr.2025.102655","DOIUrl":"10.1016/j.chempr.2025.102655","url":null,"abstract":"<div><div><span>The missing BN isostere of coronene, 2a</span><sup>1</sup>,6a<sup>1</sup>,10b<sup>1</sup>-triaza-2b,6b,10b-triborahexabenzo[<em>a</em>,<em>d</em>,<em>g</em>,<em>j</em>,<em>m</em>,<em>p</em><span>]coronene, was synthesized in a one-shot procedure from 2,4,6-tribenzhydryl-1,3,5-triazine via a dearomative triple borylation. In the crystalline state, the resulting nearly </span><em>D</em><sub>3</sub><span>-symmetric molecule forms an efficient 3D π-stacking network, with disorder observed in the B–N and C=C bonds. Density functional theory (DFT) calculations of electronic couplings predict a promising potential for applications in organic semiconducting materials. The introduction of six additional methyl groups<span> suppressed this disorder, enabling precise bond-length alternation analysis. Notably, the incorporation of three BN units into the spoke positions of the coronene core induced a paratropic ring current in the N</span></span><sub>3</sub>C<sub>3</sub><span> central ring, a hypsochromic shift in absorption and emission maxima, and an enhanced photoluminescence<span> quantum yield<span>. Furthermore, selective single and double borylations of 2,4,6-tribenzhydryl-1,3,5-triazine were demonstrated, alongside a dearomative triple borylation of its benzothiophene analog. These findings may accelerate advances in both fundamental and applied chemistry based on BN/CC isosterism.</span></span></span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102655"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102628
Bo Yang , Yixun Sun , Jiale Hu , Si Meng , Muhua Chen , Xin Wang , Min Ren , Jing Guo , Yiting Wang , Ji Li , Min Jia , Juan Fan , Huaming Sun , Jing Li , Hua Xu , Junfa Wei
Doping heteroatoms into the π-skeleton of buckybowls is a promising strategy for modulating molecular geometry and electronic structures, thereby imparting unique physicochemical properties. In this study, we present the synthesis and characterization of three bowl-shaped nitrogen-doped nanographenes, known as triazasupersumanenes, which feature a coronene core surrounded by alternating five- and six-membered rings. These typical π-bowls display deeper bowl depths, remarkable redshifts in both absorption and emission spectra, and more reversible oxidation peaks compared with their S-doped analog. Furthermore, para-substituents on N-aryls significantly influence molecular properties and exhibit intriguing characteristics, including polar crystals, reversible mechanofluorochromic (MFC) performance, open-shell diradical dication, and supramolecular recognition for fullerene C60. Despite no π⋯π interactions, the fabricated device 1a@CHCl3 exhibits unexpected p-type transport properties in organic field-effect transistor measurements. This work reveals the structure-property relationships of heterosupersumanenes, offering valuable insights into the design and synthesis of π-bowls with tunable properties and highlighting their potential as organic semiconductors.
{"title":"Triazasupersumanenes: Bowl-shaped nanographenes with tunable properties and unexpected charge transport performance","authors":"Bo Yang , Yixun Sun , Jiale Hu , Si Meng , Muhua Chen , Xin Wang , Min Ren , Jing Guo , Yiting Wang , Ji Li , Min Jia , Juan Fan , Huaming Sun , Jing Li , Hua Xu , Junfa Wei","doi":"10.1016/j.chempr.2025.102628","DOIUrl":"10.1016/j.chempr.2025.102628","url":null,"abstract":"<div><div><span>Doping heteroatoms<span><span><span> into the π-skeleton of buckybowls is a promising strategy for modulating molecular geometry and electronic structures, thereby imparting unique physicochemical properties. In this study, we present the synthesis and characterization of three bowl-shaped nitrogen-doped nanographenes, known as triazasupersumanenes, which feature a </span>coronene core surrounded by alternating five- and six-membered rings. These typical π-bowls display deeper bowl depths, remarkable redshifts in both absorption and </span>emission spectra, and more reversible oxidation peaks compared with their S-doped analog. Furthermore, </span></span><em>para</em><span>-substituents on N-aryls significantly influence molecular properties and exhibit intriguing characteristics, including polar crystals, reversible mechanofluorochromic (MFC) performance, open-shell diradical dication, and supramolecular recognition for fullerene C</span><sub>60</sub>. Despite no π⋯π interactions, the fabricated device <strong>1a@CHCl</strong><sub><strong>3</strong></sub> exhibits unexpected <em>p</em>-type transport properties in organic field-effect transistor measurements. This work reveals the structure-property relationships of heterosupersumanenes, offering valuable insights into the design and synthesis of π-bowls with tunable properties and highlighting their potential as organic semiconductors.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102628"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329262","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102828
Olli Ikkala
In the August 7 issue of Science, Liu and colleagues report a co-crystallization strategy for inorganic-polymer hybrids and achieve ordered interfaces for the efficient coupling of mechanical, electrical, and magnetic responses. The resulting VSe2-PVDF magnetoelectric nanocomposites enable flexible, low-energy wearable sensors with ultrafast responses, high sensitivity, and exceptional performance.
{"title":"Interfacial co-crystallization: An emerging approach in composite film design","authors":"Olli Ikkala","doi":"10.1016/j.chempr.2025.102828","DOIUrl":"10.1016/j.chempr.2025.102828","url":null,"abstract":"<div><div>In the August 7 issue of <em>Science</em>, Liu and colleagues report a co-crystallization strategy for inorganic-polymer hybrids and achieve ordered interfaces for the efficient coupling of mechanical, electrical, and magnetic responses. The resulting VSe<sub>2</sub>-PVDF magnetoelectric nanocomposites enable flexible, low-energy wearable sensors with ultrafast responses, high sensitivity, and exceptional performance.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102828"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145545839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102871
Sachchida Nand , Oleg V. Larionov
Direct photocatalytic decarboxylative functionalization enabled by proton-coupled electron transfer has recently emerged as a synthetically versatile strategy for the functionalization of carboxylic acids. In the Journal of the American Chemical Society, Mitsunuma, Kanai, and co-workers demonstrate that an azanthaquinone photocatalytic system can overcome the challenging decarboxylation of aromatic and perfluoroalkyl carboxylic acids, expanding the horizon of photoinduced decarboxylation into new synthetic domains.
{"title":"Azaanthraquinones redefine the scope of photocatalytic PCET for direct decarboxylative functionalization","authors":"Sachchida Nand , Oleg V. Larionov","doi":"10.1016/j.chempr.2025.102871","DOIUrl":"10.1016/j.chempr.2025.102871","url":null,"abstract":"<div><div>Direct photocatalytic decarboxylative functionalization enabled by proton-coupled electron transfer has recently emerged as a synthetically versatile strategy for the functionalization of carboxylic acids. In the <em>Journal of the American Chemical Society</em>, Mitsunuma, Kanai, and co-workers demonstrate that an azanthaquinone photocatalytic system can overcome the challenging decarboxylation of aromatic and perfluoroalkyl carboxylic acids, expanding the horizon of photoinduced decarboxylation into new synthetic domains.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102871"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102870
Virgil Percec
This Backstory presents the author’s perspective on the discovery of covalent dendrimers. Between 1979 and 1985, four laboratories across academia and industry reported the first syntheses of branched and monodisperse-protein-like covalent macromolecules, prepared from synthetic and biological building blocks. These branched molecules and macromolecules were described under four different names, which were initially debated but ultimately accepted by the scientific community. The advent of dendrimers established a new research field that is now supported by two biannual international symposia.
{"title":"The 40th anniversary of covalent dendrimers","authors":"Virgil Percec","doi":"10.1016/j.chempr.2025.102870","DOIUrl":"10.1016/j.chempr.2025.102870","url":null,"abstract":"<div><div>This Backstory presents the author’s perspective on the discovery of covalent dendrimers. Between 1979 and 1985, four laboratories across academia and industry reported the first syntheses of branched and monodisperse-protein-like covalent macromolecules, prepared from synthetic and biological building blocks. These branched molecules and macromolecules were described under four different names, which were initially debated but ultimately accepted by the scientific community. The advent of dendrimers established a new research field that is now supported by two biannual international symposia.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102870"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145719000","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102875
Tom Jan Smak
On October 13–15, 2025, the Cell Symposium “Chemical solutions for a sustainable plastics future” was organized in partnership with Utrecht University. This interdisciplinary meeting covered topics ranging from polymer synthesis and recycling to micro-nanoplastics, social science, and policy. Across this spectrum, lectures were given by leading experts in their fields.
{"title":"Chemical solutions for a sustainable plastics future","authors":"Tom Jan Smak","doi":"10.1016/j.chempr.2025.102875","DOIUrl":"10.1016/j.chempr.2025.102875","url":null,"abstract":"<div><div>On October 13–15, 2025, the Cell Symposium “Chemical solutions for a sustainable plastics future” was organized in partnership with Utrecht University. This interdisciplinary meeting covered topics ranging from polymer synthesis and recycling to micro-nanoplastics, social science, and policy. Across this spectrum, lectures were given by leading experts in their fields.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102875"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145719001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102652
Guodong Li , Guoxun Ji , Shunshun Xiong , Zhen Jiang , Mengjia Yuan , Fuwan Zhai , Shujing Lin , Lixi Chen , Chunyi Yu , Mingrui Zuo , Xia Wang , Zhiyong Peng , Benxian Huang , Nannan Shen , Lanhua Chen , Yanlong Wang , Xihai Li , Xuanjun Wang , Xiaofeng Fang , Congwei Wu , Shuao Wang
The disposal of radioactive xenon and krypton generated by nuclear fission is essential for the zero emission of nuclear energy, while their efficient capture at low concentrations remains a daunting challenge. We present here a design philosophy for noble gas uptake by introducing the concept of the confinement-intensified multi-heavy-atom effect derived from the Lennard-Jones 12–6 potential, which is achieved by the construction of a previously unnoticed structural unit of a tetrahedral halogen cage arranged in a metal-organic framework (Cu(idc-I)). Record-high adsorption capacities of 128.58 and 20.83 cm3 cm−3 for Xe and Kr, respectively, were achieved at 0.1 bar and ambient temperature, along with the highest Kr Henry coefficient (10.19 mmol cm−3 bar−1). The dense tandem-arrayed tetrahedral iodine cages, as powerful binding sites have been visualized by in situ single-crystal X-ray diffraction studies and theoretical simulations, endowing Cu(idc-I) with the ability to effectively capture trace Xe and Kr from mimic nuclear reprocessing off-gas.
{"title":"Confinement-intensified multi-heavy-atom effect in a tetrahedral iodine cage enables unprecedented capture of trace xenon and krypton","authors":"Guodong Li , Guoxun Ji , Shunshun Xiong , Zhen Jiang , Mengjia Yuan , Fuwan Zhai , Shujing Lin , Lixi Chen , Chunyi Yu , Mingrui Zuo , Xia Wang , Zhiyong Peng , Benxian Huang , Nannan Shen , Lanhua Chen , Yanlong Wang , Xihai Li , Xuanjun Wang , Xiaofeng Fang , Congwei Wu , Shuao Wang","doi":"10.1016/j.chempr.2025.102652","DOIUrl":"10.1016/j.chempr.2025.102652","url":null,"abstract":"<div><div><span><span>The disposal of radioactive xenon and </span>krypton<span><span> generated by nuclear fission is essential for the zero emission of nuclear energy, while their efficient capture at low concentrations remains a daunting challenge. We present here a design philosophy for </span>noble gas uptake by introducing the concept of the confinement-intensified multi-heavy-atom effect derived from the Lennard-Jones 12–6 potential, which is achieved by the construction of a previously unnoticed structural unit of a tetrahedral halogen cage arranged in a metal-organic framework (Cu(idc-I)). Record-high adsorption capacities of 128.58 and 20.83 cm</span></span><sup>3</sup> cm<sup>−3</sup> for Xe and Kr, respectively, were achieved at 0.1 bar and ambient temperature, along with the highest Kr Henry coefficient (10.19 mmol cm<sup>−3</sup> bar<sup>−1</sup>). The dense tandem-arrayed tetrahedral iodine cages, as powerful binding sites have been visualized by <em>in situ</em><span> single-crystal X-ray diffraction studies and theoretical simulations, endowing Cu(idc-I) with the ability to effectively capture trace Xe and Kr from mimic nuclear reprocessing off-gas.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102652"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102650
Matthew J. Evans , Dat T. Nguyen , Joseph M. Parr , Jeremy Mullins , Rahul Mondal , Thayalan Rajeshkumar , Laurent Maron , Cameron Jones
The only molecular allotrope of phosphorus, white phosphorus, P4, is shown to coordinate to main-group metal centers, forming stable complexes, for the first time. Coordinatively unsaturated, Lewis acidic magnesium(II) complexes, Mg(EtNONAr) (EtNONAr; Ar = TCHP, 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene, or Ar = DCHP, 4,5-bis(2,6-dicyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) react with P4 to form 1:1 and 2:1 Lewis adducts, Mg(EtNONTCHP)(η2-P4) and {Mg(EtNONDCHP)}2(μ-η2:η2-P4), respectively. The related arene-capped complexes of the heavier alkaline earth metals, M(EtNONTCHP)(η6-toluene) (M = Ca, Sr), also engage in coordination with P4 to give M(EtNONTCHP)(η6-toluene)(η1-P4). These alkaline earth metal-P4 complexes appear to reversibly bind P4 in aliphatic solvents and dissociate P4 upon dissolution in aromatic solvents. Reduction of P4 by magnesium(I) complex K2{Mg(tBuNONTrip)}2 (tBuNONTrip = 4,5-bis(2,4,6-triisopropylanilido)-2,7-di(tert-butyl)-9,9-dimethyl-xanthene) and a magnesium(I) synthon K2{Mg(EtNONTCHP)}2(μ-N2) provides entry to the planar, aromatic P42– dianion in K2{Mg(RNONAr)}2(μ-P4) (R = tBu, Ar = Trip; R = Et, Ar = TCHP), the hydrolysis of which releases PH3.
磷的唯一同素异形体，白磷，P4，首次被证明与主基团金属中心配位，形成稳定的配合物。配位不饱和刘易斯酸性镁（II）配合物Mg(EtNONAr) (EtNONAr；Ar = chp, 4,5-二（2,4,6-三环己基苯胺）-2,7-二乙基-9,9-二甲基-杂蒽，或Ar = DCHP, 4,5-二（2,6-二环己基苯胺）-2,7-二乙基-9,9-二甲基杂蒽)与P4反应，分别生成1:1和2:1的Lewis加成物Mg(EtNONTCHP)（η2-P4）和{Mg(EtNONDCHP)}2（μ-η2:η2-P4）。与之相关的较重碱土金属芳烃包盖配合物M(EtNONTCHP)（η - 6-甲苯）（M = Ca, Sr）也与P4配合生成M(EtNONTCHP)（η - 6-甲苯）（η - 1-P4）。这些碱土金属-P4配合物似乎在脂肪类溶剂中可逆地结合P4，并在芳香类溶剂中溶解P4。镁(I)配合物K2{Mg(tBuNONTrip)}2 （tBuNONTrip = 4,5-二（2,4,6-三异丙基苯基）-2,7-二（叔丁基）-9,9-二甲基-杂蒽）和镁(I)合成物K2{Mg(EtNONTCHP)}2（μ-N2）还原P4提供了进入K2{Mg(RNONAr)}2（μ-P4）中的平面芳香P42 - diion (R = tBu, Ar = Trip；R = Et, Ar = TCHP)，其水解释放PH3。
{"title":"Neutral P4 coordination and reduction at alkaline earth metal centers","authors":"Matthew J. Evans , Dat T. Nguyen , Joseph M. Parr , Jeremy Mullins , Rahul Mondal , Thayalan Rajeshkumar , Laurent Maron , Cameron Jones","doi":"10.1016/j.chempr.2025.102650","DOIUrl":"10.1016/j.chempr.2025.102650","url":null,"abstract":"<div><div>The only molecular allotrope of phosphorus, white phosphorus, P<sub>4</sub>, is shown to coordinate to main-group metal centers, forming stable complexes, for the first time. Coordinatively unsaturated, Lewis acidic magnesium(II) complexes, Mg(<sup>Et</sup>NON<sup>Ar</sup>) (<sup>Et</sup>NON<sup>Ar</sup>; Ar = TCHP, 4,5-bis(2,4,6-tricyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene, or Ar = DCHP, 4,5-bis(2,6-dicyclohexylanilido)-2,7-diethyl-9,9-dimethyl-xanthene) react with P<sub>4</sub><span> to form 1:1 and 2:1 Lewis adducts, Mg(</span><sup>Et</sup>NON<sup>TCHP</sup>)(η<sup>2</sup>-P<sub>4</sub>) and {Mg(<sup>Et</sup>NON<sup>DCHP</sup>)}<sub>2</sub>(μ-η<sup>2</sup>:η<sup>2</sup>-P<sub>4</sub><span>), respectively. The related arene-capped complexes of the heavier alkaline earth metals, M(</span><sup>Et</sup>NON<sup>TCHP</sup>)(η<sup>6</sup>-toluene) (M = Ca, Sr), also engage in coordination with P<sub>4</sub> to give M(<sup>Et</sup>NON<sup>TCHP</sup>)(η<sup>6</sup>-toluene)(η<sup>1</sup>-P<sub>4</sub>). These alkaline earth metal-P<sub>4</sub> complexes appear to reversibly bind P<sub>4</sub> in aliphatic solvents and dissociate P<sub>4</sub><span> upon dissolution in aromatic solvents. Reduction of P</span><sub>4</sub> by magnesium(I) complex K<sub>2</sub>{Mg(<sup><em>t</em>Bu</sup>NON<sup>Trip</sup>)}<sub>2</sub> (<sup><em>t</em>Bu</sup>NON<sup>Trip</sup> = 4,5-bis(2,4,6-triisopropylanilido)-2,7-di(tert-butyl)-9,9-dimethyl-xanthene) and a magnesium(I) synthon K<sub>2</sub>{Mg(<sup>Et</sup>NON<sup>TCHP</sup>)}<sub>2</sub>(<em>μ</em>-N<sub>2</sub>) provides entry to the planar, aromatic P<sub>4</sub><sup>2–</sup> dianion in K<sub>2</sub>{Mg(<sup>R</sup>NON<sup>Ar</sup>)}<sub>2</sub>(<em>μ</em>-P<sub>4</sub>) (R = tBu, Ar = Trip; R = Et, Ar = TCHP), the hydrolysis of which releases PH<sub>3</sub>.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102650"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144547539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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