Structural Chemistry最新文献

{"title":"Atomic and molecular volumes from three crystal tessellations: a comparison of the QTAIM, Hirshfeld, and Voronoi data","authors":"Anna V. Vologzhanina","doi":"10.1007/s11224-024-02426-x","DOIUrl":"10.1007/s11224-024-02426-x","url":null,"abstract":"<div><p>The volumes of atoms and molecules obtained by means of quantum theory of atoms in molecules (V_AM) in previously reported π and σ complexes were compared with those revealed from the Hirshfeld surfaces (V_HS) and the Voronoi tessellation (V_VD). For metal atoms, V_HS and V_VD are close to V_AM values. The Voronoi tessellation underestimates volumes of heavy and low-coordinated metal atoms by 27% in average, while for s- and d-metal ions in σ-complexes V_VD deviates from V_AM by 6% in average only. The Hirshfeld surfaces underestimate volumes of metal atoms in π-complexes by 17% and overestimate those in σ-complexes by 30% in average. Any correlation between atomic volumes of non-metals is absent; however, V_HS and V_VD values for polyatomic (even diatomic) molecules deviated from V_AM by 11% in average. All three methods indicate constancy of molecular volumes in crystals. Sensitivity of three methods to detect trends in atomic and molecular volumes over different datasets was discussed.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"113 - 123"},"PeriodicalIF":2.1,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142963007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Leon N Cooper (1930 − 2024) — physicist Nobel laureate for superconductivity and molecular neurologist","authors":"Istvan Hargittai","doi":"10.1007/s11224-024-02416-z","DOIUrl":"10.1007/s11224-024-02416-z","url":null,"abstract":"","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"381 - 383"},"PeriodicalIF":2.1,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142963146","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"How physicists became biologists","authors":"Istvan Hargittai","doi":"10.1007/s11224-024-02400-7","DOIUrl":"10.1007/s11224-024-02400-7","url":null,"abstract":"<div><p>There have been three periods in physicists moving to biology. First, a few distinguished physicists recognized early the need and possibilities for applying their approach to biology. Then, Erwin Schrödinger’s <i>What is Life?</i> induced a good number of scientists to seek the next frontier of science in biology. The trend has continued in recent time; thus, we are living the third period. For a few scientists, their path to biology is looked at in some detail. The peculiar case of outstanding physicists salvaging biology in the Soviet Union is mentioned. So is the world-famous Cavendish Laboratory initiating what has become a leading venue of biological research. Broad-based education fosters scientists’ ability to change their main line of enquiry.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"1 - 12"},"PeriodicalIF":2.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142963011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anchoring of boron halides BX (X: F, Cl, and Br) on transition metal (M: Cr, Mo, W) carbonyl complexes M(CO)5 (M: Cr, Mo, W): structure, bonding, and energy decomposition studies based on theoretical calculations","authors":"Favour A. Nelson,&nbsp;Rawlings A. Timothy,&nbsp;Terkumbur E. Gber,&nbsp;Jisha M. Thomas,&nbsp;Thayalaraj Christopher Jeyakumar,&nbsp;Emmanuel Emmanuel","doi":"10.1007/s11224-024-02406-1","DOIUrl":"10.1007/s11224-024-02406-1","url":null,"abstract":"<div><p>This study investigates the structural and electronic properties of hexacarbonyl [M(CO)₆] (M = Cr, Mo, W) and haloborylene-substituted complexes [M(CO)₅BX] (X = F, Cl, Br) using the density functional theory (DFT) computation at the B3LYP-D3(BJ)/def2-SVP method. The M-C bond lengths are found to follow the order: W–C (2.090 Å in W(CO)₅BBr) &gt; Mo-C (2.055 Å) &gt; Cr-C (1.906 Å in Cr(CO)₅BCl). Substituting BX leads to a decrease in bond lengths and an increase in bond strength for Cr complexes, while Mo and W complexes show opposite trends. The M-B bond lengths increase from Cr (1.886 Å in Cr(CO)₅BBr) to W (2.115 Å in W(CO)₅BF), indicating a correlation with atomic radii and electronic interactions. Vibrational spectroscopy shows C-O stretching frequencies ranging from 2080 to 2210 cm⁻¹, with Cr(CO)₆ at 2208 cm⁻¹, while B-X stretching frequencies range from 1045 to 1456 cm⁻¹. The Wiberg bond order (WBO) analysis indicates strong bonding in Mo(CO)₅BCl (WBO = 1.234) and weaker bonds in bromide complexes, consistent with intrinsic bond strength values. A charge decomposition analysis reveals significant back-donation in Cr(CO)₅BBr, while Mo(CO)₆ favors σ-donation. Thermodynamic calculations show that bromide complexes exhibit high stability with negative entropy changes and elevated heat capacities. Quantum chemical parameters reveal that Cr(CO)₆ has the highest HOMO–LUMO gap (5.475 eV), whereas W(CO)₅BBr shows the smallest (4.372 eV), indicating greater reactivity. QTAIM analysis shows consistent electron density (ρ = 0.291–0.292 a.u.) and a Laplacian value of − 0.232, confirming similar electronic distributions. This comprehensive analysis elucidates the structural stability, bonding characteristics, and electronic properties of these complexes, providing insights into their potential catalytic applications.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"13 - 28"},"PeriodicalIF":2.1,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142962964","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The “reaction zone” concept in modeling solid-state transformations and predicting crystal structures","authors":"Ekaterina O. Bukhteeva,&nbsp;Vladislav A. Blatov","doi":"10.1007/s11224-024-02402-5","DOIUrl":"10.1007/s11224-024-02402-5","url":null,"abstract":"<div><p>We propose a new approach to determine a reaction zone in solid substances. The reaction zone of an origin atom A is defined as a region surrounded by the atoms, which can interact with A without forming self-crossings in the crystal structure network. The identification of this region is based on the topological characteristics of the free space and is essentially independent of its geometry which allows one to apply this model to different types of structures. The reaction zone can be determined by either constructing cages of the natural tiling, i.e., the partition of the crystal space by minimal cages, or analyzing the intersections of the smallest rings of connected atoms by potential interatomic contacts. The proposed approach enables one to determine the atoms to be available for interactions in a crystal structure, thus facilitating the analysis of mechanisms of solid-state transformations and the modeling of novel solid phases. We have applied this approach to generate two new sp³-hybridized carbon allotropes from 150 three-coordinated parent periodic nets. Our analysis of the natural tilings in these allotropes as well as in 1661 carbon allotropes from the SACADA database shows that the structures possessing an isohedral tiling and/or tiles with six-membered faces exhibit high hardness. The allotropes described by similar tilings demonstrate comparable mechanical properties.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"77 - 87"},"PeriodicalIF":2.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142963115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stabilization of cyclo-N6 by insertion into [18]-annulene: a DFT study","authors":"Fabio Pichierri","doi":"10.1007/s11224-024-02394-2","DOIUrl":"10.1007/s11224-024-02394-2","url":null,"abstract":"<div><p>The elusiveness of hexazine (a.k.a. hexaazabenzene) and its perhydrogenated derivative, hexazinane, prompted the author of this paper to investigate the possibility of stabilizing the six-membered nitrogen ring by inserting it into [18]-annulene. The resulting compound is made of a central N₆ ring surrounded by an outer ring of 18 carbon atoms that prevents its decomposition into dinitrogen. The N₆ ring is non-planar and with a chair-like conformation that does not undergo conformational isomerization. The designed molecule can be stabilized either by oxidation to a hexa-oxide derivative or by coordination of ZnCl⁺. Furthermore, a triangle-shaped macrocyclic isomer made of three pyridazine moieties connected to each other by ethylene bridges represents a possible precursor in the synthesis of the N₆-embedded hydrocarbon. By employing an alkali or alkaline-earth metal cation that coordinates the three pyridazine monomers it becomes possible to bring their nitrogen atoms in close proximity so that a subsequent aromatic fusion reaction could be attempted.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"2055 - 2064"},"PeriodicalIF":2.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142540755","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aromatic terminology. Highlighting the keywords polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic compounds (PACs)","authors":"Israel Agranat","doi":"10.1007/s11224-024-02395-1","DOIUrl":"10.1007/s11224-024-02395-1","url":null,"abstract":"<div><p>The present <i>Review</i> on aromatic terminology was prompted by a recent series of articles exploring the chemical space of polycyclic aromatic systems and introducing new related keywords. The keywords polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic compounds (PACs) are highlighted. Keywords and other entities relevant to PAHs and PACs are outlined. The article calls the community of polycyclic aromatic hydrocarbons and polycyclic aromatic compounds to use these two leading keywords and their acronyms PAHs and PACs and the accompanying keyword benzenoid hydrocarbons, but to refrain from using and coining related new and previously proposed similar general keywords. This recommendation does not rule out keywords combining ‘polycyclic aromatic’ and a specific functionality, e.g., polycyclic aromatic ketones.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"73 - 75"},"PeriodicalIF":2.1,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-024-02395-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142963101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular insights into genistein-NSAID hybrids—synthesis, characterisation and DFT study","authors":"Kacper Kossakowski,&nbsp;Justyna Żwawiak,&nbsp;Alina Cherniienko,&nbsp;Lucjusz Zaprutko,&nbsp;Anna Pawełczyk","doi":"10.1007/s11224-024-02377-3","DOIUrl":"10.1007/s11224-024-02377-3","url":null,"abstract":"<div><p>Genistein (GEN) is one of the pharmaceutically valuable phenolic compounds, which belongs to the isoflavone group of flavonoids and is a natural phytohormone found mainly in soybeans and red clover. It affects estrogen receptors, functioning as a selective estrogen receptor modulator (SERM) with anti-inflammatory and antioxidant activity. The presence of reactive phenolic groups in genistein provides an opportunity to expand its structure by introducing components responsible for anti-inflammatory properties. Such an innovative combination of a compound with anticancer and antioxidant potential with an anti-inflammatory compound (NSAID) may lead to interesting new derivatives with dual mechanisms of biological action. The synthesis and characterisation of genistein-NSAID hybrid compounds (ibuprofen, ketoprofen, naproxen, flurbiprofen) was conducted, together with a comprehensive structural and quantum chemistry DFT (density functional theory) computational analysis allowing the description of ¹H-NMR and ¹³C-NMR spectroscopic properties of the starting compounds and the resulting hybrids. The study resulted in the formation of seven hybrid GEN-NSAID derivatives. In the case of ibuprofen, ketoprofen and flurbiprofen, a mixture of isomeric hybrid GEN-4’-NSAID and GEN-7-NSAID derivatives was obtained, whereas, for naproxen, only GEN-4’-NSAID was formed. The structural characteristics of the resulting compounds were determined using MS, IR, ¹H-NMR and ¹³C-NMR spectroscopic methods. The most accurate DFT computational methods for predicting ¹H-NMR and ¹³C-NMR spectra were also established with statistical parameters to assess their accuracy.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"55 - 72"},"PeriodicalIF":2.1,"publicationDate":"2024-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-024-02377-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142963052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Theoretical study of novel antipyrine derivatives as promising corrosion inhibitors for mild steel in an acidic environment","authors":"Christopher Ikechukwu Ekeocha,&nbsp;Ikechukwu Nelson Uzochukwu,&nbsp;Ikenna Benedict Onyeachu,&nbsp;Ini-Ibehe Nabuk Etim,&nbsp;Emeka Emmanuel Oguzie","doi":"10.1007/s11224-024-02368-4","DOIUrl":"10.1007/s11224-024-02368-4","url":null,"abstract":"<div><p>The research delved into studying the anti-corrosive capabilities of newly developed antipyrine derivatives for mild steel in an acidic environment through density functional theory (DFT) and molecular dynamic (MD) simulation. The results of DFT calculations indicated that the newly designed antipyrine molecules exhibited high E_HOMO (− 4.788, − 4.908, and − 4.942) and low E_LUMO (− 2.339, − 3.109, and − 3.101) and energy gap (2.449, 1.799, and 1.841) for compound A1, A2, and A3, respectively. This suggests their propensity to transfer and accept electrons during molecular interaction with the alloy surface, promoting adsorption and corrosion protection. The antipyrine molecules were also noted to contain numerous electron-rich sites around the heteroatoms, functional groups, and inherent aromatic rings within their structures which helps in facilitating molecular interaction with the metal, leading to the adsorption, and formation of a protective layer for effective corrosion protection. High AlogP values (3.74 to 5.00) strongly indicate the molecules' hydrophilic nature, coating ability, and propensity to disperse water molecules and chloride ions in the corrosive system. The MD simulations also revealed high energy of adsorption, which follows a decreasing trend of A2 (− 161.00 kcal⋅mol⁻¹) &gt; A1 (− 157.15 kcal⋅mol⁻¹) &gt; A3 (− 107.93 kcal⋅mol⁻¹) indicating strong and spontaneous adsorption with a flat orientation on the Fe(110) surface. The radial distribution function (RDF) results further supported the chemosorption nature of the inhibitor molecule, and the formation of robust bonds with Fe(110) with all calculated RDF values falling below 3.5 Å. Inclusively, the investigated antipyrine compounds exhibited strong anti-corrosive properties, positioning them as promising corrosion inhibitors for mild steel deployed in acidic environments.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"36 1","pages":"363 - 379"},"PeriodicalIF":2.1,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142215618","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An analogous Twisted Little Tale on the significance of unusual infrared frequencies","authors":"Israel Agranat","doi":"10.1007/s11224-024-02376-4","DOIUrl":"10.1007/s11224-024-02376-4","url":null,"abstract":"<div><p>The autobiographical 2024 <i>Brief Report</i> published in <i>Structural Chemistry</i> by the heterocyclic chemist Professor José Elguero prompted the author to describe his recollections of a similar yet twisted little tale of an incident occurred in 1964 during his Organic Chemistry Ph.D. period at The Hebrew University of Jerusalem. The <i>trait d’union</i> between the two tales is the significance of unusual infrared frequencies in the characterization of newly synthesized organic compounds. The absence of an infrared band at the 1800–1900 cm⁻¹ region was a sufficient condition for ruling out a cyclopropanone structure (Elguero’s little tale). The presence of such an infrared band was a necessary condition for the presence of a triafulvene and triapentafulvalene systems (author’s twisted little tale). The related experience in the publication of Communications to the Editor articles in the <i>Journal of the American Chemical Society</i> is also described. A further teaching of the author’s tale is the importance of early learning of ethics and integrity in the scientific publication process.</p></div>","PeriodicalId":780,"journal":{"name":"Structural Chemistry","volume":"35 6","pages":"1937 - 1941"},"PeriodicalIF":2.1,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11224-024-02376-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142215620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}