{"title":"Triphenylphosphine-Modified IridiumIII, RhodiumIII, and RutheniumII Complexes to Achieve Enhanced Anticancer Selectivity by Targeting Mitochondria","authors":"Zhe Liu, Hanxiu Fu, Heqian Dong, Kangning Lai, Zhihao Yang, Chunyan Fan, Yuting Luo, Wenting Qin, Lihua Guo","doi":"10.1021/acs.inorgchem.4c03975","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03975","url":null,"abstract":"The incorporation of an organelle-targeting moiety into compounds has proven to be an effective strategy in the development of targeted anticancer drugs. We herein report the synthesis, characterization, and biological evaluation of novel triphenylphosphine-modified half-sandwich iridium<sup>III</sup>, rhodium<sup>III</sup>, and ruthenium<sup>II</sup> complexes. The primary goal was to enhance anticancer selectivity through mitochondrial targeting. All these triphenylphosphine-modified complexes exhibited promising cytotoxicity in the micromolar range (5.13–23.22) against A549 and HeLa cancer cell lines, surpassing the activity of comparative complexes that lack the triphenylphosphine moiety. Noteworthy is their good selectivity toward cancer cells compared to normal BEAS-2B cells, underscored by selectivity index ranging from 7.3 to >19.5. Mechanistically, these complexes primarily target mitochondria rather than interacting with DNA. The targeting of mitochondria and triggering mitochondrial dysfunction were confirmed using both confocal microscopy and flow cytometry. Their ability to depolarize mitochondrial membrane potential (MMP) and enhance reactive oxygen species (ROS) was observed, thereby leading to intrinsic apoptotic pathways. Moreover, these complexes lead to cell cycle arrest in the G<sub>2</sub>/M phase and demonstrated antimigration effects, significantly inhibiting the migration of A549 cells in wound-healing assays.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inorganic ChemistryPub Date : 2024-12-16Epub Date: 2024-11-27DOI: 10.1021/acs.inorgchem.4c04409
Morris Oyelowo, Jacob W Schaffner, Towhidi Illius Jeaydi, David A Blank, Christopher J Ziegler, Victor N Nemykin
{"title":"Introducing of an Unexplored Aza-BODIPY Diradicaloids with 4-(2,6-Di<i>tert</i>-butyl)phenoxyl Radicals Located in 1,7-Positions of the Aza-BODIPY Core.","authors":"Morris Oyelowo, Jacob W Schaffner, Towhidi Illius Jeaydi, David A Blank, Christopher J Ziegler, Victor N Nemykin","doi":"10.1021/acs.inorgchem.4c04409","DOIUrl":"10.1021/acs.inorgchem.4c04409","url":null,"abstract":"<p><p>We have prepared and characterized two diradicaloid systems <b>5a</b> and <b>5b</b> that originated from the oxidation of a 1,7-(4-(2,6-di-<i>tert</i>-butyl)phenol)-substituted aza-BODIPY core. The aza-BODIPY diradicaloids were characterized by a large array of experimental and computational methods. The diamagnetic closed-shell state was postulated as the ground state in solution and a solid-state with the substantial thermal population originating from both open-shell diradical and open-shell triplet states observed at room temperature. Transient absorption spectroscopy indicates fast (<10 ps) excited state deactivation pathways associated with the target compounds' diradical character in solution at room temperature. Variable-temperature <sup>1</sup>H NMR spectra indicate the solvent dependency of the diradical character in <b>5a</b> and <b>5b</b>. The diradicaloids could be stepwise reduced to the mixed-valence radical-anion and dianion states upon consequent single-electron reductions. Similarly, deprotonated 1,7-(4-(2,6-di-<i>tert</i>-butyl)phenol)-substituted aza-BODIPYs can be oxidized to the diradicaloid form. Both mixed-valence and dianionic forms exhibit an intense absorption in the NIR region. Density functional theory (DFT) and time-dependent DFT calculations were used to explain the transformations in the UV-Vis-NIR spectra of all target compounds.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"24008-24021"},"PeriodicalIF":4.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142737678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Circularly Polarized Phosphorescence Properties of Binuclear Cyclometalated Platinum(II) Complexes Bearing Axially Chiral Schiff-Base Ligands.","authors":"Masahiro Ikeshita, Itsuki Shimizu, Shinya Watanabe, Tomoki Yamada, Seika Suzuki, Shota Tanaka, Shingo Hattori, Kazuteru Shinozaki, Yoshitane Imai, Takashi Tsuno","doi":"10.1021/acs.inorgchem.4c03675","DOIUrl":"10.1021/acs.inorgchem.4c03675","url":null,"abstract":"<p><p>The synthesis, structure, and circularly polarized phosphorescence (CPP) properties of axially chiral cyclometalated binuclear platinum(II) complexes were described. A series of optically pure binuclear platinum(II) complexes were synthesized in five steps from commercially available (<i>R</i>)- or (<i>S</i>)-1,1'-bi-2-naphthol (BINOL) as starting materials. Their three-dimensional molecular structures and square-planar coordination geometries were elucidated from X-ray diffraction and 2D NMR analysis. The complexes were found to exhibit red- to near-infrared photoluminescence in solution and in the solid state. Furthermore, dilute DMSO solutions of the enantiopure samples showed red CPP with relatively high luminescence dissymmetry factor (<i>g</i><sub>lum</sub>) values. Density functional theory (DFT) calculations were conducted to examine their three-dimensional molecular conformations and photophysical properties.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"23642-23650"},"PeriodicalIF":4.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142737791","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Siyu Wang, Lin Ma, Lidong He, Danmin Liu, Yibo Wang, Changzeng Fan, Enke Liu, Cong Wang
{"title":"Research on the Structural and Magnetic Phase Transitions of CeMn2Ge2 Alloy","authors":"Siyu Wang, Lin Ma, Lidong He, Danmin Liu, Yibo Wang, Changzeng Fan, Enke Liu, Cong Wang","doi":"10.1021/acs.inorgchem.4c04248","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04248","url":null,"abstract":"Magnetic phase transitions play crucial roles in various material applications, including sensors, actuators, information storage, magnetic refrigeration, and so on. Typically, these magnetic phase transitions exhibit discontinuous first-order phase transitions. When a material undergoes a magnetic phase transition, it often exhibits simultaneous changes in both its crystal and electronic structures. However, the coupling relationship between the crystal structure and electronic structure during these phase transitions has not been well studied. This lack of understanding hinders our ability to integrate macroscopic physical phenomena with microscopic crystal and electronic structures. In this paper, we prepared single crystal and polycrystalline CeMn<sub>2</sub>Ge<sub>2</sub> alloy, which has been extensively studied in recent years as a material of skyrmions. The relationships between the magnetic phase transition and the crystal structure of CeMn<sub>2</sub>Ge<sub>2</sub> were investigated through magnetic measurements, variable-temperature X-ray diffraction (XRD), and experimental electron density analysis via the maximum entropy method (MEM). The results indicate that the antiferromagnetic phase transition at T<sub>N</sub> = 415 K is characterized by an increase in the intralayer Mn–Mn bond and a decrease in the Ge–Ge bond. More importantly, the ferromagnetic transition at T<sub>C</sub> = 315 K can be divided into two stages: the first stage involves the anisotropic transformation of Mn, and the second stage involves the electron enhancement of Mn. The combination of phase transition features and transport properties indicates strong anisotropy in CeMn<sub>2</sub>Ge<sub>2</sub>. Notably, our work reveals a coupling between a material’s physical properties, crystal structure, and electronic structure. Our study offers a new approach for determining the origin of magnetic phase transitions and the causes of their physical properties in materials at the electronic level.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Phase Engineering of Zirconia Support Promotes the Catalytic Dehydrogenation of Formic Acid by Pd Active Sites","authors":"Yuan Ren, Yuantong Liu, Shiqiang Deng, Jianxin Cao, Fei Liu, Mengqin Yao","doi":"10.1021/acs.inorgchem.4c03815","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03815","url":null,"abstract":"The development of Pd-based catalysts with outstanding activity and stability can further promote the hydrogen storage application of formic acid (FA). Regulating the support structure is an effective strategy for enhancing active sites in heterogeneous catalytic systems. This study prepared three types of nanosized ZrO<sub>2</sub> through phase engineering to support Pd metal and investigated the implications of support structure on the microenvironment of active sites, thus revealing the structure–activity relationship of the catalysts. The hollow nanoframes like Pd/ZrO<sub>2</sub>-F with a moderate t-ZrO<sub>2</sub> content exhibit remarkable stability and catalytic performance with a TOF of 1348 h<sup>–1</sup> at an ambient temperature. Density functional theory (DFT) calculations verify that the crystal phase of ZrO<sub>2</sub> can dramatically affect the metal–support interaction and change the Pd electronic state. Moreover, the dehydrogenation energy profiles reveal the synergy effect between ZrO<sub>2</sub> phases on Pd active sites in the reaction. Pd/m-ZrO<sub>2</sub> is more conducive to the dissociation of FA, and Pd/t-ZrO<sub>2</sub> has energy advantages in hydrogen recombination. This work provides a new perspective for understanding the synergistic effect of the zirconia crystal phase on formic acid dehydrogenation by Pd active sites.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"99 2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816495","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A Two-Dimensional Layered Heteropolyoxoniobate Based on Cubic Sn(IV)-Containing {Sn12Nb56O200} Cages with Good Proton Conductivity Property","authors":"Ping-Xin Wu, Yu-Jin Lin, Yan-Qiong Sun, Shou-Tian Zheng","doi":"10.1021/acs.inorgchem.4c04197","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04197","url":null,"abstract":"The first example of a Sn(IV)-containing heteropolyoxoniobate K<sub>6</sub>H<sub>18</sub>[Cu(en)<sub>2</sub>]<sub>8</sub>{[Sn(OH)<sub>2</sub>]<sub>12</sub> (HNb<sub>7</sub>O<sub>22</sub>)<sub>8</sub>}·2en·88H<sub>2</sub>O (<b>1</b>) is built from nanoscale high-nuclearity cubic {[Sn(OH)<sub>2</sub>]<sub>12</sub>(HNb<sub>7</sub>O<sub>22</sub>)<sub>8</sub>} cluster and [Cu(en)<sub>2</sub>]<sup>2+</sup> complexes. The cubic {[Sn(OH)<sub>2</sub>]<sub>12</sub>(HNb<sub>7</sub>O<sub>22</sub>)<sub>8</sub>} cage is composed of eight {Nb<sub>7</sub>O<sub>22</sub>} clusters and 12 SnO<sub>6</sub> octahedrons. The eight {Nb<sub>7</sub>O<sub>22</sub>} fragments are situated at the vertices of the cubic cage, while the 12 SnO<sub>6</sub> octahedrons are positioned along the edges of the cubic cage. The [Cu(en)<sub>2</sub>]<sup>2+</sup> complexes link the {[Sn(OH)<sub>2</sub>]<sub>12</sub>(HNb<sub>7</sub>O<sub>22</sub>)<sub>8</sub>} clusters into two-dimensional (2D) (4,4) grid-like layers. The N–H···O hydrogen bonds between the [Cu(en)<sub>2</sub>]<sup>2+</sup> complexes and the {[Sn(OH)<sub>2</sub>]<sub>12</sub>(HNb<sub>7</sub>O<sub>22</sub>)<sub>8</sub>} clusters link the layers to form a 3D supramolecular structure. Compound <b>1</b> exhibits a good proton conductivity of 3.1 × 10<sup>–2</sup> S cm<sup>–1</sup> at 85 °C and 98% relative humidity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816338","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guanlei Gao, Si-Yu Xu, Xinghui Qi, Jie-Ru Yang, Peiqi Lin, Jin Chen, Xiao-Ying Huang, Ke-Zhao Du
{"title":"Organic Ligand Exchange: The Chiral Structure-Property Regulation of Cuprous Halides.","authors":"Guanlei Gao, Si-Yu Xu, Xinghui Qi, Jie-Ru Yang, Peiqi Lin, Jin Chen, Xiao-Ying Huang, Ke-Zhao Du","doi":"10.1021/acs.inorgchem.4c03561","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03561","url":null,"abstract":"<p><p>The strategy of organic ligand exchange is proposed to tune the optical properties of organic-inorganic hybrid cuprous halides. In this work, the chiral ligand (S)-(-)-2,2'-bis(di-<i>p</i>-tolylphosphino)-1,1'-binaphthyl ((S)-Tol-BINAP) and achiral triphenylphosphine (PPh<sub>3</sub>) are introduced into cuprous halides CuX-PPh<sub>3</sub>-[(S)-Tol-BINAP] (X = Cl, Br, I) through organic ligand exchange. As a result, the mixed organic ligands can enhance second harmonic generation (SHG) and aggregation-induced emission (AIE) optical properties. Moreover, the title compounds exhibit progressively enlarged SHG effects along with heavier halogen substitution due to their stronger polarizability. In the meantime, the reduced π-π stacking interaction of the organic ligand will improve their photoluminescence quantum yield. The experimental results combined with the theoretical calculation clarify the structure-property relationship well. Furthermore, the title compounds have been developed for the application of latent fingerprint detection.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yulia N. Toikka, Anton V. Rozhkov, Sergi Burguera, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. Bokach
{"title":"Nucleophilicity of the Nitrile N Atom Whose Lone Pair Is Blocked by Metal Coordination. The π-Hole Interaction between an Arene Carbon and the Metal-Bound Nitrile Nitrogen","authors":"Yulia N. Toikka, Anton V. Rozhkov, Sergi Burguera, Antonio Frontera, Vadim Yu. Kukushkin, Nadezhda A. Bokach","doi":"10.1021/acs.inorgchem.4c03995","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03995","url":null,"abstract":"Cocrystallization of CuI with NCNMe<sub>2</sub> in the presence of substituted perfluoroarenes─iodoperfluorobenzene (IFB), 4,4′-diiodoperfluorobiphenyl (4,4′-FIBP), and 4-bromoperfluorobenzonitrile (4-BrFBN)─led to the formation of three types of adducts <b>1</b>·2(IFB), <b>1</b>·4,4’FIBP, and <b>1</b>·4-BrFBN (<b>1</b> is Cu<sub>4</sub>I<sub>4</sub>(NCNMe<sub>2</sub>)<sub>4</sub>), all studied by X-ray crystallography. In these cocrystals, the coordinated nitrile N atom (whose electron pair is engaged in metal coordination) still acts as an electron donor, forming π-hole interactions, specifically, π-hole<sub>arene</sub>···N<sub>nitrile</sub>, with the perfluoroarenes. These interactions were examined in the context of their occurrence alongside other interactions involving C atoms of the electron-deficient aromatic rings and nucleophilic atoms of the copper cluster. Comprehensive theoretical calculations, including MEP, QTAIM/NCI plot analysis, EDA, ELF projections, and ETS-NOCV calculations, revealed that the nitrile ligand N atom maintains significant negative potential and that π-hole interactions are energetically more favorable than σ-hole interactions in the studied systems. This nucleophilicity is based on a noticeable contribution of the heterocumulene form, Cu–N<sup>–</sup>═C═N<sup>+</sup>Me<sub>2</sub>, in the resonance hybrid of Cu-bound NCNMe<sub>2</sub>: a phenomenon influenced by both the coordination and the conjugation between the NR<sub>2</sub> and CN groups The discovery of π-hole<sub>arene</sub>···N<sub>nitrile</sub> contacts adds a new dimension to our understanding of coordinated push–pull nitriles, in particular dialkylcyanamides, revealing that the coordinated nitrile N atom can still function as a nucleophile in noncovalent binding.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Construction and Magnetic Difference of {CoIIICoII12MII6} (M = CoII/CdII) Aggregates with Homo- and Heterometallic Centers Derived from {Co14} Precursors","authors":"Ye Tao, Yun-Kai Chen, Huang-Fei Qin, Zhao-Ting Pan, Hai-Ye Li, Haiquan Tian, Fu-Ping Huang","doi":"10.1021/acs.inorgchem.4c04083","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04083","url":null,"abstract":"Controllable synthesis of sophisticated aggregations has attracted wide attention from scientists. In this work, homo- and heterometallic {Co<sup>III</sup>Co<sup>II</sup><sub>12</sub>M<sup>II</sup><sub>6</sub>} (<i>M</i> = Co<sup>II</sup>/Cd<sup>II</sup>) aggregates with similar skeletons, composed of two [Co<sub>3</sub>M<sub>3</sub>(dpbt)<sub>3</sub>] peripheries and a central [Co<sub>7</sub>(OH)<sub>8</sub>] vertex-fused double-cubane, were constructed from prefabricated {Co<sub>14</sub>} clusters and characterized by single-crystal X-ray diffraction and XPS, ICP-MS, SEM (EDX), and so on. And then, the structure and magnetic differences of them had been further analyzed under dotted with paramagnetic Co<sup>II</sup> ions and/or diamagnetic Cd<sup>II</sup> ions. Interestingly, the spin canting behavior in <b>{Co</b><sup><b>III</b></sup><b>Co</b><sup><b>II</b></sup><sub><b>18</b></sub><b>}</b> was suppressed in <b>{Co</b><sup><b>III</b></sup><b>Co</b><sup><b>II</b></sup><sub><b>12</b></sub><b>Cd</b><sup><b>II</b></sup><sub><b>6</b></sub><b>}</b>, upon the introducing of Cd<sup>II</sup> ions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inorganic ChemistryPub Date : 2024-12-12DOI: 10.1021/acs.inorgchem.4c0399510.1021/acs.inorgchem.4c03995
Yulia N. Toikka, Anton V. Rozhkov, Sergi Burguera, Antonio Frontera, Vadim Yu. Kukushkin and Nadezhda A. Bokach*,
{"title":"Nucleophilicity of the Nitrile N Atom Whose Lone Pair Is Blocked by Metal Coordination. The π-Hole Interaction between an Arene Carbon and the Metal-Bound Nitrile Nitrogen","authors":"Yulia N. Toikka, Anton V. Rozhkov, Sergi Burguera, Antonio Frontera, Vadim Yu. Kukushkin and Nadezhda A. Bokach*, ","doi":"10.1021/acs.inorgchem.4c0399510.1021/acs.inorgchem.4c03995","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03995https://doi.org/10.1021/acs.inorgchem.4c03995","url":null,"abstract":"<p >Cocrystallization of CuI with NCNMe<sub>2</sub> in the presence of substituted perfluoroarenes─iodoperfluorobenzene (IFB), 4,4′-diiodoperfluorobiphenyl (4,4′-FIBP), and 4-bromoperfluorobenzonitrile (4-BrFBN)─led to the formation of three types of adducts <b>1</b>·2(IFB), <b>1</b>·4,4’FIBP, and <b>1</b>·4-BrFBN (<b>1</b> is Cu<sub>4</sub>I<sub>4</sub>(NCNMe<sub>2</sub>)<sub>4</sub>), all studied by X-ray crystallography. In these cocrystals, the coordinated nitrile N atom (whose electron pair is engaged in metal coordination) still acts as an electron donor, forming π-hole interactions, specifically, π-hole<sub>arene</sub>···N<sub>nitrile</sub>, with the perfluoroarenes. These interactions were examined in the context of their occurrence alongside other interactions involving C atoms of the electron-deficient aromatic rings and nucleophilic atoms of the copper cluster. Comprehensive theoretical calculations, including MEP, QTAIM/NCI plot analysis, EDA, ELF projections, and ETS-NOCV calculations, revealed that the nitrile ligand N atom maintains significant negative potential and that π-hole interactions are energetically more favorable than σ-hole interactions in the studied systems. This nucleophilicity is based on a noticeable contribution of the heterocumulene form, Cu–N<sup>–</sup>═C═N<sup>+</sup>Me<sub>2</sub>, in the resonance hybrid of Cu-bound NCNMe<sub>2</sub>: a phenomenon influenced by both the coordination and the conjugation between the NR<sub>2</sub> and CN groups The discovery of π-hole<sub>arene</sub>···N<sub>nitrile</sub> contacts adds a new dimension to our understanding of coordinated push–pull nitriles, in particular dialkylcyanamides, revealing that the coordinated nitrile N atom can still function as a nucleophile in noncovalent binding.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"63 51","pages":"24210–24221 24210–24221"},"PeriodicalIF":4.3,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142875010","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}