{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T04:49:43Z","timestamp":1787028583977,"version":"build-2736575974"},"reference-count":105,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2026,7,22]],"date-time":"2026-07-22T00:00:00Z","timestamp":1784678400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Int. J. Mol. Sci.","IJMS"],"abstract":"<jats:p>Halogen bonding develops when an electrophilic region associated with a covalently bonded halogen interacts attractively with a nucleophilic site on another same or different molecular entity. Here, we show that in many crystals in the Cambridge Structural Database, the intermolecular distances and directional features of F\u00b7\u00b7\u00b7F close contacts involve \u03c3-hole-like regions on covalently bound fluorine. However, such interactions cannot readily be classified as classical halogen bonds, as the interacting fluorine atoms may lack a positive site (e.g., a positive \u03c3-hole). In this context, we investigated directional F\u00b7\u00b7\u00b7F interactions involving HF, CH4\u2212nFn (n = 1\u20134), and C6H6\u2212nFn (n = 1\u20136) interacting with negative sites in the same or different partner interacting species using computational methods, which exhibit complex geometries reminiscent of \u03c3-hole interactions. However, such interactions between sites of like polarity are more appropriately described as \u03c3-hole-centered anti-electrostatic interaction motifs, driven in part by dispersion, rather than being recognized as conventional \u03c3-hole-centered halogen bonds. This interpretation is supported by molecular electrostatic surface potential and symmetry-adapted perturbation theory analyses.<\/jats:p>","DOI":"10.3390\/ijms27146519","type":"journal-article","created":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T01:01:28Z","timestamp":1784768488000},"page":"6519","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Negative \u03c3-Holes on Fluorine in Molecules Revisited: Halogen Bonding or Counterintuitive, Anti-Electrostatic Interactions?"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7102-3133","authenticated-orcid":false,"given":"Pradeep R.","family":"Varadwaj","sequence":"first","affiliation":[{"name":"Institute of Physics, Faculty of Physics, Astronomy, and Informatics, Nicolaus Copernicus University in Toru\u0144, 87-100 Toru\u0144, Poland"},{"name":"Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1675-3835","authenticated-orcid":false,"given":"Helder M.","family":"Marques","sequence":"additional","affiliation":[{"name":"Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg 2050, South Africa"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5661-5659","authenticated-orcid":false,"given":"Ireneusz","family":"Grabowski","sequence":"additional","affiliation":[{"name":"Institute of Physics, Faculty of Physics, Astronomy, and Informatics, Nicolaus Copernicus University in Toru\u0144, 87-100 Toru\u0144, Poland"},{"name":"Institute of Advanced Studies, Nicolaus Copernicus University in Toru\u0144, ul. Wile\u0144ska 4, 87-100 Toru\u0144, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mohd. Mudassir","family":"Husain","sequence":"additional","affiliation":[{"name":"Department of Applied Sciences and Humanities, Faculty of Engineering and Technology, Jamia Millia Islamia, New Delhi 110025, India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2026,7,22]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"756","DOI":"10.1126\/science.abq0516","article-title":"Electron in a cube: Synthesis and characterization of perfluorocubane as an electron acceptor","volume":"377","author":"Sugiyama","year":"2022","journal-title":"Science"},{"key":"ref_2","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Varadwaj, A., and Marques, H.M. (2019). Halogen Bonding: A Halogen-Centered Noncovalent Interaction Yet to Be Understood. Inorganics, 7.","DOI":"10.3390\/inorganics7030040"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"225","DOI":"10.1002\/open.201900337","article-title":"Halogen Bonding in Two-Dimensional Crystal Engineering","volume":"9","author":"Teyssandier","year":"2020","journal-title":"ChemistryOpen"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"5669","DOI":"10.1039\/c1cs15027h","article-title":"Alternative DNA base-pairs: From efforts to expand the genetic code to potential material applications","volume":"40","author":"Wojciechowski","year":"2011","journal-title":"Chem. Soc. Rev."},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Desiraju, G.R., and Steiner, T. (2000). The Weak Hydrogen Bond in Structural Chemistry and Biology, Oxford University Press.","DOI":"10.1093\/acprof:oso\/9780198509707.001.0001"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1942","DOI":"10.1021\/acschembio.0c00292","article-title":"Quantifying Intramolecular Halogen Bonds in Nucleic Acids: A Combined Protein Data Bank and Theoretical Study","volume":"15","author":"Frontera","year":"2020","journal-title":"ACS Chem. Biol."},{"key":"ref_7","unstructured":"R, M., Kubinyi, H., Folkers, G., Carloni, P., and Alber, F. (2003). The Use of the Molecular Electrostatic Potential in Medicinal Chemistry. Quantum Medicinal Chemistry, Wiley-VCH."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"1363","DOI":"10.1021\/jm3012068","article-title":"Principles and Applications of Halogen Bonding in Medicinal Chemistry and Chemical Biology","volume":"56","author":"Wilcken","year":"2013","journal-title":"J. Med. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2478","DOI":"10.1021\/acs.chemrev.5b00484","article-title":"The Halogen Bond","volume":"116","author":"Cavallo","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_10","unstructured":"Rissanen, K. (2021). Chapter 6\u2014From molecular electrostatic potential surfaces to practical avenues for directed assembly of organic and metal-containing crystalline materials. Hot Topics in Crystal Engineering, Elsevier."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1038\/s41598-018-36218-1","article-title":"Significance of hydrogen bonding and other noncovalent interactions in determining octahedral tilting in the CH3NH3PbI3 hybrid organic-inorganic halide perovskite solar cell semiconductor","volume":"9","author":"Varadwaj","year":"2019","journal-title":"Sci. Rep."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"10650","DOI":"10.1038\/s41598-019-46725-4","article-title":"C70 Fullerene Cage as a Novel Catalyst for Efficient Proton Transfer Reactions between Small Molecules: A Theoretical study","volume":"9","author":"Varadwaj","year":"2019","journal-title":"Sci. Rep."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Marques, H.M., Varadwaj, A., Grabowski, I., and Yamashita, K. (2026). Molecular Electrostatic Surface Potential: A Predictive Framework for Noncovalent Interactions and Adsorption Characteristics in Molecular Entities. Int. J. Mol. Sci., 27.","DOI":"10.3390\/ijms27083352"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"565","DOI":"10.1021\/ar010054t","article-title":"Hydrogen Bridges in Crystal Engineering:\u2009 Interactions without Borders","volume":"35","author":"Desiraju","year":"2002","journal-title":"Acc. Chem. Res."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"203","DOI":"10.1107\/S2052520617001809","article-title":"Experimental investigation of halogen-bond hard-soft acid-base complementarity","volume":"73","author":"Riel","year":"2017","journal-title":"Acta Crystallogr. B"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1107\/S2052520616003954","article-title":"The Cambridge Structural Database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Cryst. B"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"3559","DOI":"10.1039\/C5PY00354G","article-title":"Halogen bonding in polymer science: From crystal engineering to functional supramolecular polymers and materials","volume":"6","author":"Berger","year":"2015","journal-title":"Polym. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"7118","DOI":"10.1021\/cr500674c","article-title":"Halogen Bonding in Supramolecular Chemistry","volume":"115","author":"Gilday","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"3830","DOI":"10.1002\/anie.201713012","article-title":"Iodine(III) Derivatives as Halogen Bonding Organocatalysts","volume":"57","author":"Heinen","year":"2018","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"8645","DOI":"10.1039\/C6CC03638D","article-title":"Halogen bonding anion recognition","volume":"52","author":"Brown","year":"2016","journal-title":"Chem. Commun."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"12800","DOI":"10.1039\/D1DT02414K","article-title":"Anion recognition by halogen bonding and hydrogen bonding bis(triazole)-imidazolium [2]rotaxanes","volume":"50","author":"Turner","year":"2021","journal-title":"Dalton Trans."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1711","DOI":"10.1351\/PAC-REC-12-05-10","article-title":"Definition of the halogen bond (IUPAC Recommendations 2013)","volume":"85","author":"Desiraju","year":"2013","journal-title":"Pure Appl. Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1889","DOI":"10.1515\/pac-2018-0713","article-title":"Definition of the chalcogen bond (IUPAC Recommendations 2019)","volume":"91","author":"Aakeroy","year":"2019","journal-title":"Pure Appl. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"1411","DOI":"10.1039\/D2CE01621D","article-title":"Definition of the tetrel bond","volume":"25","author":"Varadwaj","year":"2023","journal-title":"CrystEngComm"},{"key":"ref_25","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., and Yamashita, K. (2022). Definition of the Pnictogen Bond: A Perspective. Inorganics, 10.","DOI":"10.3390\/inorganics10100149"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1515\/pac-2020-1002","article-title":"Definition of the pnictogen bond (IUPAC Recommendations 2023)","volume":"96","author":"Resnati","year":"2024","journal-title":"Pure Appl. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"291","DOI":"10.1007\/s00894-006-0130-2","article-title":"Halogen bonding: The \u03c3-hole","volume":"13","author":"Clark","year":"2007","journal-title":"J. Mol. Model."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"32166","DOI":"10.1039\/C7CP06793C","article-title":"The \u03c3-hole revisited","volume":"19","author":"Politzer","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"7340","DOI":"10.1002\/anie.201502571","article-title":"Aerogen Bonding Interaction: A New Supramolecular Force?","volume":"54","author":"Frontera","year":"2015","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Grabarz, A., Michalczyk, M., Zierkiewicz, W., and Scheiner, S. (2021). Anion-Anion Interactions in Aerogen-Bonded Complexes. Influence of Solvent Environment. Molecules, 26.","DOI":"10.3390\/molecules26082116"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"24748","DOI":"10.1039\/C5CP03272E","article-title":"\u03c0-Hole aerogen bonding interactions","volume":"17","author":"Frontera","year":"2015","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"391","DOI":"10.1002\/open.202000323","article-title":"A Quantitative Molecular Orbital Perspective of the Chalcogen Bond","volume":"10","author":"Hamlin","year":"2021","journal-title":"ChemistryOpen"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"19969","DOI":"10.1039\/C9CP03783G","article-title":"The chalcogen bond: Can it be formed by oxygen?","volume":"21","author":"Varadwaj","year":"2019","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Varadwaj, A., Marques, H.M., and Yamashita, K. (2022). Chalcogen Bonding in the Molecular Dimers of WCh2 (Ch = S, Se, Te): On the Basic Understanding of the Local Interfacial and Interlayer Bonding Environment in 2D Layered Tungsten Dichalcogenides. Int. J. Mol. Sci., 23.","DOI":"10.3390\/ijms23031263"},{"key":"ref_35","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Marques, H.M., Varadwaj, A., and Yamashita, K. (2022). Chalcogen\u00b7\u00b7\u00b7Chalcogen Bonding in Molybdenum Disulfide, Molybdenum Diselenide and Molybdenum Ditelluride Dimers as Prototypes for a Basic Understanding of the Local Interfacial Chemical Bonding Environment in 2D Layered Transition Metal Dichalcogenides. Inorganics, 10.","DOI":"10.3390\/inorganics10010011"},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"e202303641","DOI":"10.1002\/chem.202303641","article-title":"Chalcogen and Hydrogen Bond Team up in Driving Anion\u22c5\u22c5\u22c5Anion Self-Assembly","volume":"30","author":"Beccaria","year":"2024","journal-title":"Chem. Eur. J."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Alkorta, I., and Legon, A.C. (2018). An Ab Initio Investigation of the Geometries and Binding Strengths of Tetrel-, Pnictogen-, and Chalcogen-Bonded Complexes of CO2, N2O, and CS2 with Simple Lewis Bases: Some Generalizations. Molecules, 23.","DOI":"10.3390\/molecules23092250"},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Varadwaj, A., Marques, H.M., and Yamashita, K. (2022). The Phosphorus Bond, or the Phosphorus-Centered Pnictogen Bond: The Covalently Bound Phosphorus Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor. Molecules, 27.","DOI":"10.3390\/molecules27051487"},{"key":"ref_39","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., and Yamashita, K. (2022). The Stibium Bond or the Antimony-Centered Pnictogen Bond: The Covalently Bound Antimony Atom in Molecular Entities in Crystal Lattices as a Pnictogen Bond Donor. Int. J. Mol. Sci., 23.","DOI":"10.3390\/ijms23094674"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1038","DOI":"10.1039\/D2CE01620F","article-title":"The pnictogen bond forming ability of bonded bismuth atoms in molecular entities in the crystalline phase: A perspective","volume":"25","author":"Varadwaj","year":"2023","journal-title":"CrystEngComm"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"80","DOI":"10.3390\/compounds2010007","article-title":"The Nitrogen Bond, or the Nitrogen-Centered Pnictogen Bond: The Covalently Bound Nitrogen Atom in Molecular Entities and Crystals as a Pnictogen Bond Donor","volume":"2","author":"Varadwaj","year":"2022","journal-title":"Compounds"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"1486","DOI":"10.1002\/cphc.201800023","article-title":"Revealing Factors Influencing the Fluorine-Centered Non-Covalent Interactions in Some Fluorine-Substituted Molecular Complexes: Insights from First-Principles Studies","volume":"19","author":"Varadwaj","year":"2018","journal-title":"ChemPhysChem"},{"key":"ref_43","first-page":"609","article-title":"Fluorine prefers hydrogen bonds over halogen bonds! Insights from crystal structures of some halofluorobenzenes","volume":"229","author":"Sathishkumar","year":"2014","journal-title":"Z. Krist."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"7748","DOI":"10.1039\/c004189k","article-title":"Halogen bonding: An electrostatically-driven highly directional noncovalent interaction","volume":"12","author":"Politzer","year":"2010","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"278","DOI":"10.1002\/cphc.201200799","article-title":"Halogen Bonding: An Interim Discussion","volume":"14","author":"Politzer","year":"2013","journal-title":"ChemPhysChem"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"1494","DOI":"10.1039\/D5CE00838G","article-title":"Investigation of noncovalent interactions in organofluorine compounds with C\u2013F bonds in different electronic environments","volume":"28","author":"Das","year":"2026","journal-title":"CrystEngComm"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"e202400724","DOI":"10.1002\/cphc.202400724","article-title":"Quantitative Characterization of Fluorine-Centered Noncovalent Interactions in Crystalline Benzanilides","volume":"26","author":"Shukla","year":"2025","journal-title":"ChemPhysChem"},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"2574","DOI":"10.1021\/nn505876n","article-title":"Extended Halogen Bonding between Fully Fluorinated Aromatic Molecules","volume":"9","author":"Kawai","year":"2015","journal-title":"ACS Nano"},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"3309","DOI":"10.1007\/s00894-011-1015-6","article-title":"Halogen bond tunability I: The effects of aromatic fluorine substitution on the strengths of halogen-bonding interactions involving chlorine, bromine, and iodine","volume":"17","author":"Riley","year":"2011","journal-title":"J. Mol. Model."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"31624","DOI":"10.1039\/C5CP03209A","article-title":"Unusual bonding modes of perfluorobenzene in its polymeric (dimeric, trimeric and tetrameric) forms: Entirely negative fluorine interacting cooperatively with entirely negative fluorine","volume":"17","author":"Varadwaj","year":"2015","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"19098","DOI":"10.1039\/C5RA27039A","article-title":"Can an entirely negative fluorine in a molecule, viz. perfluorobenzene, interact attractively with the entirely negative site(s) on another molecule(s)? Like liking like!","volume":"6","author":"Varadwaj","year":"2016","journal-title":"RSC Adv."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"2943","DOI":"10.1021\/acs.cgd.9b01565","article-title":"New Theoretical Insight into Fluorination and Fluorine\u2013Fluorine Interactions as a Driving Force in Crystal Structures","volume":"20","year":"2020","journal-title":"Cryst. Growth Des."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"20381","DOI":"10.1039\/C6CP03862J","article-title":"Electrostatically enhanced F\u00b7\u00b7\u00b7F interactions through hydrogen bonding, halogen bonding and metal coordination: An ab initio study","volume":"18","author":"Frontera","year":"2016","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"99","DOI":"10.1021\/acs.jpcc.9b09428","article-title":"Fluorine\u00b7\u00b7\u00b7Fluorine Interactions in a High-Pressure Layered Phase of Perfluorobenzene","volume":"124","author":"Rusek","year":"2020","journal-title":"J. Phys. Chem. C"},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"1201","DOI":"10.1002\/cphc.202100202","article-title":"Can Counter-Intuitive Halogen Bonding Be Coulombic?","volume":"22","author":"Murray","year":"2021","journal-title":"ChemPhysChem"},{"key":"ref_56","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Marques, H.M., and Varadwaj, P.R. (2019). Is the Fluorine in Molecules Dispersive? Is Molecular Electrostatic Potential a Valid Property to Explore Fluorine-Centered Non-Covalent Interactions?. Molecules, 24.","DOI":"10.3390\/molecules24030379"},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1002\/qua.24877","article-title":"Fluorines in tetrafluoromethane as halogen bond donors: Revisiting address the nature of the fluorine\u2019s \u03c3hole","volume":"115","author":"Varadwaj","year":"2015","journal-title":"Int. J. Quantum Chem."},{"key":"ref_58","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., and Yamashita, K. (2018). Comment on \u201cExtended Halogen Bonding between Fully Fluorinated Aromatic Molecules: Kawai et al., ACS Nano, 2015, 9, 2574\u201d. arXiv.","DOI":"10.1021\/nn505876n"},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"7290","DOI":"10.1021\/acs.jpca.0c06803","article-title":"F-Halogen Bond: Conditions for Its Existence","volume":"124","author":"Scheiner","year":"2020","journal-title":"J. Phys. Chem. A"},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"4739","DOI":"10.1002\/chem.201405054","article-title":"Does fluorine participate in halogen bonding?","volume":"21","author":"Eskandari","year":"2015","journal-title":"Chem. Eur. J."},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"6964","DOI":"10.1039\/D1CP05628J","article-title":"Search for an exothermic halogen bond between anions","volume":"24","author":"Scheiner","year":"2022","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_62","doi-asserted-by":"crossref","first-page":"870","DOI":"10.1002\/cphc.202000098","article-title":"On the Stability of Interactions between Pairs of Anions\u2014Complexes of MCl3\u2212 (M=Be, Mg, Ca, Sr, Ba) with Pyridine and CN\u2212","volume":"21","author":"Zierkiewicz","year":"2020","journal-title":"ChemPhysChem"},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"e202401030","DOI":"10.1002\/cphc.202401030","article-title":"Solid-State NMR Spectroscopy of Organic Periodates Featuring Halogen Bonded IO4\u2212\u2009\u00b7\u00b7\u00b7\u2009IO4\u2212 Adducts","volume":"26","author":"Beccaria","year":"2025","journal-title":"ChemPhysChem"},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"e202300298","DOI":"10.1002\/cphc.202300298","article-title":"Halogen Bonding Assembles Anion\u00b7\u00b7\u00b7Anion Architectures in Non-centrosymmetric Iodate and Bromate Crystals","volume":"24","author":"Calabrese","year":"2023","journal-title":"ChemPhysChem"},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"226","DOI":"10.1107\/S1600576719014092","article-title":"Mercury 4.0: From visualization to analysis, design and prediction","volume":"53","author":"Macrae","year":"2020","journal-title":"J. Appl. Cryst."},{"key":"ref_66","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2016). Gaussian 16 Rev. C.01, Gaussian, Inc."},{"key":"ref_67","unstructured":"Keith, T.A. (2019). AimAll (V. 19.10.12), TK Gristmill Software. Available online: https:\/\/aim.tkgristmill.com."},{"key":"ref_68","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. Comp. Chem."},{"key":"ref_69","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_70","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"1165","DOI":"10.1142\/S0219633612500770","article-title":"Assessment of the performance of the M05-class and M06-class functionals for the structure and geometry of hydrogen-bonded and halogen-bonded complexes","volume":"11","author":"Zhang","year":"2012","journal-title":"J. Theor. Comput. Chem."},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"1045","DOI":"10.1021\/ci600510j","article-title":"Basis Set Exchange: A Community Database for Computational Sciences","volume":"47","author":"Schuchardt","year":"2007","journal-title":"J. Chem. Inf. Model."},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"3754","DOI":"10.1073\/pnas.79.12.3754","article-title":"Electrostatic potential molecular surfaces","volume":"79","author":"Weiner","year":"1982","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_74","doi-asserted-by":"crossref","first-page":"1720","DOI":"10.1021\/acs.jpca.9b09992","article-title":"Microhydration of a Carbonyl Group: How does the Molecular Electrostatic Potential (MESP) Impact the Formation of (H2O)n:(R2C\u2550O) Complexes?","volume":"124","author":"Zins","year":"2020","journal-title":"J. Phys. Chem. A"},{"key":"ref_75","doi-asserted-by":"crossref","unstructured":"Politzer, P., Lane, P., and Murray, J.S. (2016). Electrostatic Potentials, Intralattice Attractive Forces and Crystal Densities of Nitrogen-Rich C,H,N,O Salts. Crystals, 6.","DOI":"10.3390\/cryst6010007"},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1021\/ar00109a003","article-title":"Atoms in molecules","volume":"18","author":"Bader","year":"1985","journal-title":"Acc. Chem. Res."},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"724","DOI":"10.1002\/cphc.201701325","article-title":"The Independent Gradient Model: A New Approach for Probing Strong and Weak Interactions in Molecules from Wave Function Calculations","volume":"19","author":"Lefebvre","year":"2018","journal-title":"ChemPhysChem"},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"231","DOI":"10.1002\/cmtd.202100007","article-title":"Interaction Region Indicator: A Simple Real Space Function Clearly Revealing Both Chemical Bonds and Weak Interactions","volume":"1","author":"Lu","year":"2021","journal-title":"Chem.\u2013Methods"},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"094106","DOI":"10.1063\/1.4867135","article-title":"Levels of symmetry adapted perturbation theory (SAPT). I. Efficiency and performance for interaction energies","volume":"140","author":"Parker","year":"2014","journal-title":"J. Chem. Phys."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"084114","DOI":"10.1063\/5.0275311","article-title":"Levels of symmetry-adapted perturbation theory (SAPT). II. Convergence of interaction energy components","volume":"163","author":"Schriber","year":"2025","journal-title":"J. Chem. Phys."},{"key":"ref_81","doi-asserted-by":"crossref","first-page":"184108","DOI":"10.1063\/5.0006002","article-title":"PSI4 1.4: Open-source software for high-throughput quantum chemistry","volume":"152","author":"Smith","year":"2020","journal-title":"J. Chem. Phys."},{"key":"ref_82","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Varadwaj, A., and Marques, H.M. (2020). Does Chlorine in CH3Cl Behave as a Genuine Halogen Bond Donor?. Crystals, 10.","DOI":"10.3390\/cryst10030146"},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"5494","DOI":"10.1021\/acs.cgd.4c00228","article-title":"Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit","volume":"24","author":"Varadwaj","year":"2024","journal-title":"Cryst. Growth Des."},{"key":"ref_84","doi-asserted-by":"crossref","unstructured":"Politzer, P., and Murray, J.S. (2017). \u03c3-Hole Interactions: Perspectives and Misconceptions. Crystals, 7.","DOI":"10.3390\/cryst7070212"},{"key":"ref_85","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1016\/j.comptc.2012.06.007","article-title":"Perspectives on halogen bonding and other \u03c3-hole interactions: Lex parsimoniae (Occam\u2019s Razor)","volume":"998","author":"Politzer","year":"2012","journal-title":"Comput. Theor. Chem."},{"key":"ref_86","first-page":"267","article-title":"Molecular Surfaces, van der Waals Radii and Electrostatic Potentials in Relation to Noncovalent Interactions","volume":"82","author":"Murray","year":"2009","journal-title":"Croat. Chem. Acta"},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"e1326","DOI":"10.1002\/wcms.1326","article-title":"Molecular electrostatic potentials and noncovalent interactions","volume":"7","author":"Murray","year":"2017","journal-title":"WIREs Comput. Mol. Sci."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"464","DOI":"10.1002\/jcc.24891","article-title":"\u03c3-holes and \u03c0-holes: Similarities and differences","volume":"39","author":"Politzer","year":"2018","journal-title":"J. Comput. Chem."},{"key":"ref_89","doi-asserted-by":"crossref","unstructured":"Politzer, P., and Murray, J.S. (2019). \u03c3-Holes vs. Buildups of Electronic Density on the Extensions of Bonds to Halogen Atoms. Inorganics, 7.","DOI":"10.3390\/inorganics7060071"},{"key":"ref_90","doi-asserted-by":"crossref","first-page":"3746","DOI":"10.1021\/jp511118s","article-title":"Double Hole\u2013Lump Interaction between Halogen Atoms","volume":"119","author":"Duarte","year":"2015","journal-title":"J. Phys. Chem. A"},{"key":"ref_91","doi-asserted-by":"crossref","first-page":"9","DOI":"10.1016\/j.cplett.2010.04.021","article-title":"Halogen bonding: A lump\u2013hole interaction","volume":"492","author":"Eskandari","year":"2010","journal-title":"Chem. Phys. Lett."},{"key":"ref_92","doi-asserted-by":"crossref","first-page":"343","DOI":"10.1002\/jcc.25125","article-title":"Do surfaces of positive electrostatic potential on different halogen derivatives in molecules attract? like attracting like!","volume":"39","author":"Varadwaj","year":"2018","journal-title":"J. Comput. Chem."},{"key":"ref_93","doi-asserted-by":"crossref","first-page":"878","DOI":"10.1021\/cm00043a002","article-title":"New Precursors for Barium Metal-Organic Chemical Vapor Deposition. In Situ Growth of Epitaxial Barium Titanate Films Using a Liquid Barium Precursor","volume":"6","author":"Neumayer","year":"1994","journal-title":"Chem. Mater."},{"key":"ref_94","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1016\/j.poly.2012.01.001","article-title":"Syntheses and coordination studies of 2-(diphenylphosphinomethyl)pyridine and its oxide towards mercury(II)","volume":"34","author":"Padron","year":"2012","journal-title":"Polyhedron"},{"key":"ref_95","doi-asserted-by":"crossref","first-page":"427","DOI":"10.1016\/S0020-1693(02)01042-3","article-title":"Interligand interactions affecting specific metal bonding to nucleic acid bases. A case of [Rh2(OAc)4], [Rh2(HNOCCF3)4], and [Rh2(OAc)2(HNOCCF3)2] toward purine nucleobases and nucleosides","volume":"339","author":"Aoki","year":"2002","journal-title":"Inorg. Chim. Acta"},{"key":"ref_96","doi-asserted-by":"crossref","first-page":"1683","DOI":"10.1002\/(SICI)1521-3773(20000502)39:9<1683::AID-ANIE1683>3.0.CO;2-1","article-title":"A Highly Soluble Luminescent Decanuclear Gold(I) Complex with a Propeller-Shaped Structure","volume":"39","author":"Yam","year":"2000","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_97","doi-asserted-by":"crossref","first-page":"8617","DOI":"10.1039\/c3dt50599e","article-title":"A cartography of the van der Waals territories","volume":"42","author":"Alvarez","year":"2013","journal-title":"Dalton Trans."},{"key":"ref_98","doi-asserted-by":"crossref","unstructured":"Qui\u00f1onero, D., and Frontera, A. (2019). Hydrogen Bond versus Halogen Bond in HXOn (X = F, Cl, Br, and I) Complexes with Lewis Bases. Inorganics, 7.","DOI":"10.3390\/inorganics7010009"},{"key":"ref_99","doi-asserted-by":"crossref","first-page":"21824","DOI":"10.1021\/acsomega.0c02887","article-title":"Unconventional Type III Halogen\u00b7\u00b7\u00b7Halogen Interactions: A Quantum Mechanical Elucidation of \u03c3-Hole\u00b7\u00b7\u00b7\u03c3-Hole and Di-\u03c3-Hole Interactions","volume":"5","author":"Ibrahim","year":"2020","journal-title":"ACS Omega"},{"key":"ref_100","doi-asserted-by":"crossref","first-page":"539","DOI":"10.1002\/jcc.26812","article-title":"Independent gradient model based on Hirshfeld partition: A new method for visual study of interactions in chemical systems","volume":"43","author":"Lu","year":"2022","journal-title":"J. Comp. Chem."},{"key":"ref_101","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1039\/b206867b","article-title":"Distance criteria for crystal packing analysis of supramolecular motifs","volume":"27","author":"Dance","year":"2003","journal-title":"New J. Chem."},{"key":"ref_102","doi-asserted-by":"crossref","unstructured":"Varadwaj, P.R., Varadwaj, A., Marques, H.M., and Yamashita, K. (2018). Can Combined Electrostatic and Polarization Effects Alone Explain the F\u00b7\u00b7\u00b7F Negative-Negative Bonding in Simple Fluoro-Substituted Benzene Derivatives? A First-Principles Perspective. Computation, 6.","DOI":"10.3390\/computation6040051"},{"key":"ref_103","doi-asserted-by":"crossref","first-page":"579","DOI":"10.1002\/cphc.201900968","article-title":"Electrostatics and Polarization in \u03c3- and \u03c0-Hole Noncovalent Interactions: An Overview","volume":"21","author":"Politzer","year":"2020","journal-title":"ChemPhysChem"},{"key":"ref_104","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., Jezierska, B., Grabowski, I., Husain, M.M., and Yamashita, K. (2026). Anti-Electrostatic Anion-Anion Noncovalent Interactions Are Not Halogen Bonds: Evidence from X\u00b7\u00b7\u00b7O Contacts in XO4\u2212 Dimers and Oligomers in Crystals Structures. Int. J. Mol. Sci., 27.","DOI":"10.3390\/ijms27125267"},{"key":"ref_105","doi-asserted-by":"crossref","unstructured":"Varadwaj, A., Varadwaj, P.R., Marques, H.M., Grabowski, I., Yamashita, K., and Husain, M.M. (2026). Halogen Bonds or Not? Reassessing Noncovalent Interactions in Crystals of Periodate Anion from the Cambridge Structural Database. Molecules, 31.","DOI":"10.3390\/molecules31122153"}],"container-title":["International Journal of Molecular Sciences"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1422-0067\/27\/14\/6519\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,7,23]],"date-time":"2026-07-23T01:02:31Z","timestamp":1784768551000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1422-0067\/27\/14\/6519"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,22]]},"references-count":105,"journal-issue":{"issue":"14","published-online":{"date-parts":[[2026,7]]}},"alternative-id":["ijms27146519"],"URL":"https:\/\/doi.org\/10.3390\/ijms27146519","relation":{},"ISSN":["1422-0067"],"issn-type":[{"value":"1422-0067","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,22]]}}}