{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,11]],"date-time":"2026-05-11T20:31:50Z","timestamp":1778531510949,"version":"3.51.4"},"reference-count":67,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2024,10,16]],"date-time":"2024-10-16T00:00:00Z","timestamp":1729036800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Babe\u0219-Bolyai University","award":["36615\/25.11.2022"],"award-info":[{"award-number":["36615\/25.11.2022"]}]},{"name":"Babe\u0219-Bolyai University","award":["SRG-UBB 32920\/22.06.2023"],"award-info":[{"award-number":["SRG-UBB 32920\/22.06.2023"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The current study investigates the influence of several R substituents (e.g., Me, SiH3, F, Cl, Br, OH, NH2, etc.) on the aromaticity of borazine, also known as the \u201cinorganic benzene\u201d. By performing hybrid DFT methods, blended with several computational techniques, e.g., Natural Bond Orbital (NBO), Quantum Theory of Atoms in Molecules (QTAIM), Gauge-Including Magnetically Induced Current (GIMIC), Nucleus-Independent Chemical Shift (NICS), and following a simultaneous evaluation of four different aromaticity indices (para-delocalization index (PDI), multi-centre bond order (MCBO), ring current strength (RCS), and NICS parameters), it is emphasized that the aromatic character of B-substituted (B3R3N3H3) and N-substituted (B3H3N3R3) borazine derivatives can be tailored by modulating the electronic effects of R groups. It is also highlighted that the position of R substituents on the ring structure is crucial in tuning the aromaticity. Systematic comparisons of calculated aromaticity index values (i.e., via regression analyses and correlation matrices) ensure that the reported trends in aromaticity variation are accurately described, while the influence of different R groups on electron delocalization and related aromaticity phenomena is quantitatively assessed based on NBO analyses. The most relevant interactions impacting the aromatic character of investigated systems are (i) the electron conjugations occurring between the p lone pair electrons (LP) on the F, Cl, Br, O or N atoms, of R groups, and the \u03c0*(B=N) orbitals on the borazine ring (i.e., LP(R)\u2192\u03c0*(B=N) donations), and (ii) the steric-exchange (Pauli) interactions between the same LP and the \u03c0(B=N) bonds (i.e., LP(R)\u2194\u03c0(B=N) repulsions), while inductive\/field effects influence the aromaticity of the investigated trisubstituted borazine systems to a much lesser extent. This work highlights that although the aromatic character of borazine can be enhanced by grafting electron-donor substituents (F, OH, NH2, O\u2212, NH\u2212) on the N atoms, the stabilization due to aromaticity has only a moderate impact on these systems. By replacing the H substituents on the B atoms with similar R groups, the aromatic character of borazine is decreased due to strong exocyclic LP(R)\u2192\u03c0*(B=N) donations affecting the delocalization of \u03c0-electrons on the borazine ring.<\/jats:p>","DOI":"10.3390\/molecules29204902","type":"journal-article","created":{"date-parts":[[2024,10,16]],"date-time":"2024-10-16T10:11:04Z","timestamp":1729073464000},"page":"4902","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["In-Depth Theoretical Investigations of Borazine\u2019s Aromaticity: Tailoring Electron Delocalization through Substituent Effects"],"prefix":"10.3390","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0009-0005-9110-3105","authenticated-orcid":false,"given":"Alex-Cristian","family":"Tomut","sequence":"first","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering, Department of Chemistry, Babe\u0219-Bolyai University, 1 M. Kogalniceanu Street, 400084 Cluj-Napoca, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3041-8032","authenticated-orcid":false,"given":"Ionut-Tudor","family":"Moraru","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering, Department of Chemistry, Babe\u0219-Bolyai University, 1 M. Kogalniceanu Street, 400084 Cluj-Napoca, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gabriela","family":"Nemes","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry and Chemical Engineering, Department of Chemistry, Babe\u0219-Bolyai University, 1 M. Kogalniceanu Street, 400084 Cluj-Napoca, Romania"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,10,16]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"18","DOI":"10.1511\/2015.112.18","article-title":"The Many Guises of Aromaticity","volume":"103","author":"Hoffmann","year":"2015","journal-title":"Am. Sci."},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Sol\u00e0, M. (2017). Why Aromaticity Is a Suspicious Concept? Why?. Front. Chem., 5.","DOI":"10.3389\/fchem.2017.00022"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"15488","DOI":"10.1021\/jacs.9b07926","article-title":"Revisiting Kekulene: Synthesis and Single-Molecule Imaging","volume":"141","author":"Pozo","year":"2019","journal-title":"J. Am. Chem. Soc."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"129","DOI":"10.1002\/jlac.18661370202","article-title":"Untersuchungen \u00dcber Aromatische Verbindungen Ueber Die Constitution Der Aromatischen Verbindungen. I. \u00dcber Die Constitution Der Aromatischen Verbindungen","volume":"137","year":"1866","journal-title":"Justus Liebigs Ann. Chem. Pharm."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"204","DOI":"10.1007\/BF01339530","article-title":"Quantentheoretische Beitr\u00fcge Zum Benzolproblem","volume":"70","year":"1931","journal-title":"Z. Phys."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"628","DOI":"10.1007\/BF01341936","article-title":"Quantentheoretische Beitr\u00fcge Zum Problem Der Aromatischen Und Unges\u00fcttigten Verbindungen. III","volume":"76","year":"1932","journal-title":"Z. Phys."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1604","DOI":"10.1039\/CT9252701604","article-title":"CCXI.\u2014Polynuclear Heterocyclic Aromatic Types. Part II. Some Anhydronium Bases","volume":"127","author":"Armit","year":"1925","journal-title":"J. Chem. Soc. Trans."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"2215","DOI":"10.1002\/cber.19260590907","article-title":"Borwasserstoffe, IX.: B3N3H6","volume":"59","author":"Stock","year":"1926","journal-title":"Ber. Dtsch. Chem. Ges. A"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1270","DOI":"10.1002\/anie.198712701","article-title":"Synthesis and X-ray Structure of (2,4,6-Me3C6H2BPC6H11)3: A Boron-Phosphorus Analogue of Borazine","volume":"26","author":"Dias","year":"1987","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1699","DOI":"10.1002\/anie.198816991","article-title":"Synthesis and Structure of [MeAlN(2,6-IPr2C6H3)]3: An Aluminum-Nitrogen Analogue of Borazine","volume":"27","author":"Waggoner","year":"1988","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"144","DOI":"10.1021\/ja00183a025","article-title":"Boron-Phosphorus Analogs of Benzene and Cyclobutadiene. Synthesis and Characterization of the Boraphosphabenzenes (RBPR\u2019)3 (R = Mes, Ph; R\u2019 = Ph, Mes, C6H11, Tert-Bu) and the Diphosphadiboretane (ThexylBPMes)2","volume":"111","author":"Dias","year":"1989","journal-title":"J. Am. Chem. Soc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3660","DOI":"10.1021\/ja00165a062","article-title":"Synthesis and Structural Characterization of the Cyclic Species [GeN(2,6-Iso-Pr2C6H3)]3: The First \u201cGermanazene\u201d","volume":"112","author":"Bartlett","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"49","DOI":"10.1016\/0022-328X(90)83005-5","article-title":"The Synthesis, Characterization and Some Properties of New Quasi-Aromatic Main Group Ring Systems","volume":"400","author":"Power","year":"1990","journal-title":"J. Organomet. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1001","DOI":"10.1126\/science.aab0204","article-title":"Synthesis and Characterization of P2N3\u2212: An Aromatic Ion Composed of Phosphorus and Nitrogen","volume":"348","author":"Velian","year":"2015","journal-title":"Science"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"10433","DOI":"10.1021\/jacs.6b07389","article-title":"Pnictogen\u2013Silicon Analogues of Benzene","volume":"138","author":"Seitz","year":"2016","journal-title":"J. Am. Chem. Soc."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"7239","DOI":"10.1021\/ja00095a029","article-title":"Silylene, the Most Stable Form of Silicon in Aromatic Compounds","volume":"116","author":"Nyulaszi","year":"1994","journal-title":"J. Am. Chem. Soc."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2091","DOI":"10.1021\/jp511862u","article-title":"Understanding the Properties of Inorganic Benzenes Based on \u03c0-Electron Densities","volume":"119","author":"Wu","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"e202300992","DOI":"10.1002\/chem.202300992","article-title":"Dichotomy of Delocalization\/Localization and Charge-Shift Bonding in Germanazene and Its Heavier Group 14 Analogues: A Valence Bond Study","volume":"29","author":"Jain","year":"2023","journal-title":"Chem.-Eur. J."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"24108","DOI":"10.1039\/c3ra44189j","article-title":"Substituent Effects on Cyclic Electron Delocalization in Symmetric B- and N-Trisubstituted Borazine Derivatives","volume":"3","year":"2013","journal-title":"RSC Adv."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1763","DOI":"10.1080\/00268976.2016.1145749","article-title":"Stability versus Aromaticity in Mono-Hydroxylated Borazine, 1,2-Azaborine and 1,3,2,4-Diazadiborine","volume":"114","author":"Srivastava","year":"2016","journal-title":"Mol. Phys."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"34","DOI":"10.1007\/s00894-017-3555-x","article-title":"Theoretical Study of the Effects of Substituents (F, Cl, Br, CH3, and CN) on the Aromaticity of Borazine","volume":"24","author":"Costa","year":"2018","journal-title":"J. Mol. Model."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"e25859","DOI":"10.1002\/qua.25859","article-title":"Relativistic Effects on the Ring Current Strengths of the Substituted Borazine: B3N3H6 (X = H, F, Cl, Br, I, At)","volume":"119","author":"Tiznado","year":"2019","journal-title":"Int. J. Quantum Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"197","DOI":"10.1016\/j.theochem.2005.05.020","article-title":"Substituent Effect on Molecular Geometry and Aromaticity of Symmetric B-Trisubstituted Borazine","volume":"728","author":"Miao","year":"2005","journal-title":"J. Mol. Struct. THEOCHEM"},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"91","DOI":"10.1016\/j.theochem.2004.10.062","article-title":"Theoretical Study of Borazine and Its Fluoroderivatives: Aromaticity and Cation\u2013\u03c0, Anion\u2013\u03c0 Interaction","volume":"715","author":"Miao","year":"2005","journal-title":"J. Mol. Struct. THEOCHEM"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"9410","DOI":"10.1021\/jp971144b","article-title":"Ab Initio Study of the Relative Energies and Properties of Fluoroborazines","volume":"101","author":"Parker","year":"1997","journal-title":"J. Phys. Chem. A"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"7241","DOI":"10.1021\/ja00544a011","article-title":"Importance of (p-d). pi. Bonding in the Siloxane Bond","volume":"102","author":"Oberhammer","year":"1980","journal-title":"J. Am. Chem. Soc."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1051","DOI":"10.1021\/ja00056a033","article-title":"The Role of d Functions in Correlated Wave Functions: Main Group Molecules","volume":"115","author":"Magnusson","year":"1993","journal-title":"J. Am. Chem. Soc."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1339","DOI":"10.1021\/cr00029a008","article-title":"No d Orbitals but Walsh Diagrams and Maybe Banana Bonds: Chemical Bonding in Phosphines, Phosphine Oxides, and Phosphonium Ylides","volume":"94","author":"Gilheany","year":"1994","journal-title":"Chem. Rev."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"783","DOI":"10.1021\/ed084p783","article-title":"On the Role of d Orbital Hybridization in the Chemistry Curriculum","volume":"84","author":"Galbraith","year":"2007","journal-title":"J. Chem. Educ."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2515","DOI":"10.1021\/acs.jpca.7b01208","article-title":"Bridging a Knowledge Gap from Siloxanes to Germoxanes and Stannoxanes. A Theoretical Natural Bond Orbital Study","volume":"121","author":"Moraru","year":"2017","journal-title":"J. Phys. Chem. A"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"8246","DOI":"10.1021\/acs.jpca.0c07093","article-title":"Theoretical Insights into the Structural Differences between Organic and Inorganic Amines\/Ethers","volume":"124","author":"Moraru","year":"2020","journal-title":"J. Phys. Chem. A"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"13217","DOI":"10.1039\/D2CP00869F","article-title":"Offsets between Hyperconjugations, p\u2192d Donations and Pauli Repulsions Impact the Bonding of E\u2013O\u2013E Systems. Case Study on Elements of Group 14","volume":"24","author":"Moraru","year":"2022","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"6158","DOI":"10.1063\/1.478522","article-title":"Toward Reliable Density Functional Methods without Adjustable Parameters: The PBE0 Model","volume":"110","author":"Adamo","year":"1999","journal-title":"J. Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"5829","DOI":"10.1063\/1.467146","article-title":"Fully Optimized Contracted Gaussian Basis Sets of Triple Zeta Valence Quality for Atoms Li to Kr","volume":"100","author":"Huber","year":"1994","journal-title":"J. Chem. Phys."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"134105","DOI":"10.1063\/1.3484283","article-title":"Property-Optimized Gaussian Basis Sets for Molecular Response Calculations","volume":"133","author":"Rappoport","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"29705","DOI":"10.1039\/D0RA05939K","article-title":"Searching for double \u03c3- and \u03c0-aromaticity in borazine derivatives","volume":"10","author":"Tiznado","year":"2020","journal-title":"RSC Adv."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"154104","DOI":"10.1063\/1.3382344","article-title":"A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H\u2013Pu","volume":"132","author":"Grimme","year":"2010","journal-title":"J. Chem. Phys."},{"key":"ref_38","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2013). Gaussian 09, Revision E.01, Gaussian, Inc."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"214","DOI":"10.1002\/jcc.540030212","article-title":"Optimization of Equilibrium Geometries and Transition Structures","volume":"3","author":"Schlegel","year":"1982","journal-title":"J. Comput. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"423","DOI":"10.1007\/BF00671228","article-title":"Definition of a Multicenter Bond Index","volume":"1","author":"Giambiagi","year":"1990","journal-title":"Struct. Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/jcc.22885","article-title":"Multiwfn: A Multifunctional Wavefunction Analyzer","volume":"33","author":"Lu","year":"2012","journal-title":"J. Comput. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"400","DOI":"10.1002\/chem.200390041","article-title":"The Delocalization Index as an Electronic Aromaticity Criterion: Application to a Series of Planar Polycyclic Aromatic Hydrocarbons","volume":"9","author":"Poater","year":"2003","journal-title":"Chem.-Eur. J."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"362","DOI":"10.1007\/s00214-002-0356-8","article-title":"The Calculation of Electron Localization and Delocalization Indices at the Hartree-Fock, Density Functional and Post-Hartree-Fock Levels of Theory","volume":"107","author":"Poater","year":"2002","journal-title":"Theor. Chem. Acc."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"6521","DOI":"10.1021\/jp0716132","article-title":"Properties of Aromaticity Indices Based on the One-Electron Density Matrix","volume":"111","author":"Cioslowski","year":"2007","journal-title":"J. Phys. Chem. A"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"6434","DOI":"10.1039\/C5CS00066A","article-title":"Quantifying Aromaticity with Electron Delocalisation Measures","volume":"44","author":"Feixas","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"386","DOI":"10.1002\/jcc.21621","article-title":"Performance of 3D-Space-Based Atoms-in-Molecules Methods for Electronic Delocalization Aromaticity Indices","volume":"32","author":"Heyndrickx","year":"2011","journal-title":"J. Comput. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"893","DOI":"10.1021\/cr00005a013","article-title":"A Quantum Theory of Molecular Structure and Its Applications","volume":"91","author":"Bader","year":"1991","journal-title":"Chem. Rev."},{"key":"ref_48","unstructured":"Bader, R.F.W. (1994). Atoms in Molecules, Oxford University Press."},{"key":"ref_49","unstructured":"Todd, A., and Keith, T.K. (2022, May 24). AIMAll, Available online: https:\/\/aim.tkgristmill.com\/."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"3842","DOI":"10.1021\/cr030088+","article-title":"Nucleus-Independent Chemical Shifts (NICS) as an Aromaticity Criterion","volume":"105","author":"Chen","year":"2005","journal-title":"Chem. Rev."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"6597","DOI":"10.1039\/C5CS00114E","article-title":"Magnetic Criteria of Aromaticity","volume":"44","author":"Stanger","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"3922","DOI":"10.1021\/acs.jpca.9b02083","article-title":"Reexamination of NICS\u03c0,zz: Height Dependence, Off-Center Values, and Integration","volume":"123","author":"Stanger","year":"2019","journal-title":"J. Phys. Chem. A"},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"1173","DOI":"10.1063\/1.474464","article-title":"Natural Chemical Shielding Analysis of Nuclear Magnetic Resonance Shielding Tensors from Gauge-Including Atomic Orbital Calculations","volume":"107","author":"Bohmann","year":"1997","journal-title":"J. Chem. Phys."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"8251","DOI":"10.1021\/ja00179a005","article-title":"Efficient Implementation of the Gauge-Independent Atomic Orbital Method for NMR Chemical Shift Calculations","volume":"112","author":"Wolinski","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"ref_55","unstructured":"Rahalkar, A., and Stanger, A. (2023, January 30). Aroma. Available online: https:\/\/chemistry.technion.ac.il\/en\/download-the-program-windows\/."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"3952","DOI":"10.1063\/1.1773136","article-title":"Calculation of Current Densities Using Gauge-Including Atomic Orbitals","volume":"121","author":"Sundholm","year":"2004","journal-title":"J. Chem. Phys."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"20500","DOI":"10.1039\/c1cp21812c","article-title":"The Gauge Including Magnetically Induced Current Method","volume":"13","author":"Fliegl","year":"2011","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"7124","DOI":"10.1039\/C7CP00194K","article-title":"Calculations of Current Densities for Neutral and Doubly Charged Persubstituted Benzenes Using Effective Core Potentials","volume":"19","author":"Rauhalahti","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_59","unstructured":"Weinhold, F., and Landis, C.R. (2005). Valency and Bonding A Natural Bond Orbital Donor-Acceptor Perspective, Cambridge University Press."},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1002\/wcms.51","article-title":"Natural Bond Orbital Methods","volume":"2","author":"Glendening","year":"2012","journal-title":"WIREs Comput. Mol. Sci."},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"899","DOI":"10.1021\/cr00088a005","article-title":"Intermolecular Interactions from a Natural Bond Orbital, Donor-Acceptor Viewpoint","volume":"88","author":"Reed","year":"1988","journal-title":"Chem. Rev."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"5406","DOI":"10.1063\/1.474248","article-title":"Natural Bond Orbital Analysis of Steric Interactions","volume":"107","author":"Badenhoop","year":"1997","journal-title":"J. Chem. Phys."},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"5422","DOI":"10.1063\/1.475149","article-title":"Natural Steric Analysis: Ab Initio van Der Waals Radii of Atoms and Ions","volume":"107","author":"Badenhoop","year":"1997","journal-title":"J. Chem. Phys."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1002\/(SICI)1097-461X(1999)72:4<269::AID-QUA9>3.0.CO;2-8","article-title":"Natural Steric Analysis of Internal Rotation Barriers","volume":"72","author":"Badenhoop","year":"1999","journal-title":"Int. J. Quantum Chem."},{"key":"ref_65","unstructured":"Glendening, E.D., Badenhoop, K., Reed, A.E., Carpenter, J.E., Bohmann, J.A., Morales, C.M., Karafiloglou, P., Landis, C.R., and Weinhold, F. (2018). NBO 7.0., Theoretical Chemistry Institute, University of Wisconsin."},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"2301","DOI":"10.1021\/ct900344g","article-title":"Through-Space Effects of Substituents Dominate Molecular Electrostatic Potentials of Substituted Arenes","volume":"5","author":"Wheeler","year":"2009","journal-title":"J. Chem. Theory Comput."},{"key":"ref_67","unstructured":"Dennington, R., Keith, T.A., and Millam, J.M. (2016). GaussView 6.0. 16., Semichem Inc."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/20\/4902\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T16:14:30Z","timestamp":1760112870000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/20\/4902"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,10,16]]},"references-count":67,"journal-issue":{"issue":"20","published-online":{"date-parts":[[2024,10]]}},"alternative-id":["molecules29204902"],"URL":"https:\/\/doi.org\/10.3390\/molecules29204902","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,10,16]]}}}