{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T01:25:39Z","timestamp":1760145939829,"version":"build-2065373602"},"reference-count":49,"publisher":"MDPI AG","issue":"18","license":[{"start":{"date-parts":[[2024,9,17]],"date-time":"2024-09-17T00:00:00Z","timestamp":1726531200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100000001","name":"NSF","doi-asserted-by":"publisher","award":["CHE 0957544","CHE 1464936"],"award-info":[{"award-number":["CHE 0957544","CHE 1464936"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Novel tetrafluoro-\u03bb6-sulfanyl-containing oligomers prepared by visible light-promoted addition of 1,4-(bis-chlorotetrafluoro-\u03bb6-sulfanyl) benzene or 1,3-(bis-chlorotetrafluoro-\u03bb6-sulfanyl) benzene to either 1,4-diethynyl benzene or the 1,3-diethynyl isomers form hard, stress resistant thin films on spin casting. The isomeric oligomers were utilized to establish a structure-function relationship for the mechanical properties of films prepared from the oligomers. The Young\u2019s moduli of 145-nm-thick cured films could reach 60 GPa. The measured hardnesses, between 1.57 and 2.77 GPa, were more than double those of polymethyl methacrylate (PMMA) films. Curing of the tetrafluoro-\u03bb6-sulfanyl-containing polymer films by UV irradiation resulted in coatings that exhibited remarkable hardness and modulus with good surface adhesion to silicon.<\/jats:p>","DOI":"10.3390\/molecules29184413","type":"journal-article","created":{"date-parts":[[2024,9,18]],"date-time":"2024-09-18T01:16:10Z","timestamp":1726622170000},"page":"4413","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Photocurable Hypervalent Fluorinated Sulfur Containing Thin Films with Remarkable Hardness and Modulus"],"prefix":"10.3390","volume":"29","author":[{"given":"Kelly A.","family":"Bonetti","sequence":"first","affiliation":[{"name":"Department of Chemistry, University at Albany SUNY, Albany, NY 12222, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1957-3565","authenticated-orcid":false,"given":"Deniz","family":"Rende","sequence":"additional","affiliation":[{"name":"Department of Materials Science & Engineering, Rensselaer Polytechnic Institute, Troy, NY 12180, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Michael","family":"Murphy","sequence":"additional","affiliation":[{"name":"Department of Nanoscale Science & Engineering, University at Albany SUNY, Albany, NY 12222, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"John T.","family":"Welch","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University at Albany SUNY, Albany, NY 12222, USA"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,9,17]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"461","DOI":"10.3762\/bjoc.8.53","article-title":"Discovery of practical production processes for arylsulfur pentafluorides and their higher homologs, bis- and tris-(sulfur pentafluorides): Beginning of a new era of super-trifluoromethyl arene chemistry and its industry","volume":"8","author":"Umemoto","year":"2012","journal-title":"Beilstein J. Org. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"192","DOI":"10.1016\/j.jfluchem.2014.07.017","article-title":"Effects of substitution on the reactivity of alkyl aryl tetrafluoro-\u03bb6-sulfanes","volume":"167","author":"Zhong","year":"2014","journal-title":"J. Fluor. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"526","DOI":"10.1002\/anie.201306507","article-title":"Preparation and Characterization of Alkenyl Aryl Tetrafluoro-\u03bb6-sulfanes","volume":"53","author":"Zhong","year":"2014","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"787","DOI":"10.1002\/pol.20190104","article-title":"Photosensitive Hypervalent Fluorinated Sulfur Containing Polymers for Light Sensitive Applications","volume":"58","author":"Bonetti","year":"2020","journal-title":"J. Polym. Sci."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"15200","DOI":"10.1021\/la503879v","article-title":"The Elastic Mechanical Response of Supported Thin Polymer Films","volume":"30","author":"Chung","year":"2014","journal-title":"Langmuir"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"2423","DOI":"10.1021\/acsaelm.1c00296","article-title":"Highly conductive 3D printable materials for 3D structural electronics","volume":"3","author":"Baker","year":"2021","journal-title":"ACS Appl. Electron. Mater."},{"doi-asserted-by":"crossref","unstructured":"Barszczewska-Rybarek, I.M. (2019). A guide through the dental dimethacrylate polymer network structural characterization and interpretation of physico-mechanical properties. Materials, 12.","key":"ref_7","DOI":"10.3390\/ma12244057"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"4597","DOI":"10.1021\/acs.macromol.7b00418","article-title":"50th Anniversary Perspective: Putting the Squeeze on Polymers: A Perspective on Polymer Thin Films and Interfaces","volume":"50","author":"Russell","year":"2017","journal-title":"Macromolecules"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1299","DOI":"10.1163\/156856198X00452","article-title":"Techniques and considerations for nanoindentation measurements of polymer thin film constitutive properties","volume":"12","author":"Strojny","year":"1998","journal-title":"J. Adhes. Sci. Technol."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"11762","DOI":"10.1166\/jnn.2016.13589","article-title":"Low-temperature processable, photo-curable polyimides as gate insulators for thin-film transistors","volume":"16","author":"Kim","year":"2016","journal-title":"J. Nanosci. Nanotechnol."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1526","DOI":"10.1016\/j.polymer.2007.01.044","article-title":"Evaluation and control of thiol-ene\/thiol-epoxy hybrid networks","volume":"48","author":"Carioscia","year":"2007","journal-title":"Polymer"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"54","DOI":"10.1016\/j.dyepig.2015.11.012","article-title":"Near UV-vis LED-excitable two-branched sensitizers for cationic, radical, and thiol-ene photopolymerizations","volume":"126","author":"Fang","year":"2016","journal-title":"Dye. Pigm."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1143","DOI":"10.1021\/acs.macromol.5b02512","article-title":"Thiol-Ene Linear Step-Growth Photopolymerization in Miniemulsion: Fast Rates, Redox-Responsive Particles, and Semicrystalline Films","volume":"49","author":"Jasinski","year":"2016","journal-title":"Macromolecules"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"521","DOI":"10.1016\/j.reactfunctpolym.2012.04.014","article-title":"Synthesis and properties of new photosensitive triazene and o-nitrobenzene methacrylates","volume":"72","author":"Gaud","year":"2012","journal-title":"React. Funct. Polym."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"2891","DOI":"10.1021\/ma500328r","article-title":"Kinetics of UV Irradiation Induced Chain Scission and Cross-Linking of Coumarin-Containing Polyester Ultrathin Films","volume":"47","author":"Lee","year":"2014","journal-title":"Macromolecules"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2220","DOI":"10.1021\/ie303084w","article-title":"Synthesis and Property of Water-Soluble Hyperbranched Photosensitive Polysiloxane Urethane Acrylate","volume":"52","author":"Li","year":"2013","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2300211","DOI":"10.1002\/marc.202300211","article-title":"Progress in Photocurable 3D Printing of Photosensitive Polyurethane: A Review","volume":"44","author":"Fei","year":"2023","journal-title":"Macromol. Rapid Commun."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"111883","DOI":"10.1016\/j.eurpolymj.2023.111883","article-title":"The future of visible light photoinitiators of polymerization for photocrosslinking applications","volume":"187","author":"Dumur","year":"2023","journal-title":"Eur. Polym. J."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"111988","DOI":"10.1016\/j.eurpolymj.2023.111988","article-title":"Recent advances on photoinitiating systems designed for solar photocrosslinking polymerization reactions","volume":"189","author":"Dumur","year":"2023","journal-title":"Eur. Polym. J."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"68","DOI":"10.1016\/j.matpr.2022.11.342","article-title":"A review on recent development and application of radiation curing","volume":"82","author":"Kumar","year":"2023","journal-title":"Mater. Today Proc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"134843","DOI":"10.1016\/j.cej.2022.134843","article-title":"Recent advances in UV\/thermal curing silicone polymers","volume":"435","author":"Jiang","year":"2022","journal-title":"Chem. Eng. J."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"817","DOI":"10.1038\/nmat3115","article-title":"The conflicts between strength and toughness","volume":"10","author":"Ritchie","year":"2011","journal-title":"Nat. Mater."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"S456","DOI":"10.1016\/j.jallcom.2011.11.031","article-title":"Characterization of Kevlar-29 fibers by tensile tests and nanoindentation","volume":"536","year":"2012","journal-title":"J. Alloys Compd."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"031925","DOI":"10.1063\/1.2234648","article-title":"Elastic modulus of polystyrene film from near surface to bulk measured by nanoindentation using atomic force microscopy","volume":"89","author":"Miyake","year":"2006","journal-title":"Appl. Phys. Lett."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"687","DOI":"10.1016\/S1359-6462(99)00421-2","article-title":"Thickness dependence of elastic modulus and hardness of on-wafer low-k ultrathin polytetrafluoroethylene films","volume":"42","author":"Wang","year":"2000","journal-title":"Scr. Mater."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2836","DOI":"10.1073\/pnas.1618508114","article-title":"Tolerance to structural disorder and tunable mechanical behavior in self-assembled superlattices of polymer-grafted nanocrystals","volume":"114","author":"Gu","year":"2017","journal-title":"Proc. Natl. Acad. Sci. USA."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1800618","DOI":"10.1002\/admt.201800618","article-title":"State-of-the-Art and Future Challenges of UV Curable Polymer-Based Smart Materials for Printing Technologies","volume":"4","author":"Oliveira","year":"2019","journal-title":"Adv. Mater. Technol."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"2641","DOI":"10.1166\/jnn.2016.11090","article-title":"Synthesis and characterization of thermally stable photocurable polymer with cyclohexane moiety","volume":"16","author":"Kim","year":"2016","journal-title":"J. Nanosci. Nanotechnol."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"847","DOI":"10.1016\/j.apsusc.2012.07.143","article-title":"Super-hydrophilic surfaces by photo-induced micro-folding","volume":"259","author":"Bahners","year":"2012","journal-title":"Appl. Surf. Sci."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1714","DOI":"10.3938\/jkps.61.1714","article-title":"Fabrication of a bilayer wire grid polarizer in the near infrared wavelength region by using a UV curing nanoimprinting method","volume":"61","author":"Lee","year":"2012","journal-title":"J. Korean Phys. Soc."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"5067","DOI":"10.1039\/c1nr10883b","article-title":"Development of a mass-producible on-chip plasmonic nanohole array biosensor","volume":"3","author":"Nakamoto","year":"2011","journal-title":"Nanoscale"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"1879","DOI":"10.1557\/jmr.2018.78","article-title":"Photocrosslinking of low band-gap conjugated polymers using alkyl chloride sidechains: Toward high-efficiency, thermally stable polymer solar cells","volume":"33","author":"Zhang","year":"2018","journal-title":"J. Mater. Res."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"1285","DOI":"10.1002\/macp.201200066","article-title":"Direct Nanopatterning Into Conjugated Polymers Using Interference Crosslinking","volume":"213","author":"Zhang","year":"2012","journal-title":"Macromol. Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"43532","DOI":"10.1002\/app.43532","article-title":"Nanomechanical study of polymer-polymer thin film interface under applied service conditions","volume":"133","author":"Mallikarjunachari","year":"2016","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"133","DOI":"10.1002\/(SICI)1097-0126(199802)45:2<133::AID-PI969>3.0.CO;2-F","article-title":"The use of UV irradiation in polymerization","volume":"45","author":"Decker","year":"1998","journal-title":"Polym. Int."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1564","DOI":"10.1557\/JMR.1992.1564","article-title":"An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments","volume":"7","author":"Oliver","year":"1992","journal-title":"J. Mater. Res."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"613","DOI":"10.1557\/JMR.1992.0613","article-title":"On the generality of the relationship among contact stiffness, contact area, and elastic modulus during indentation","volume":"7","author":"Pharr","year":"1992","journal-title":"J. Mater. Res."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"257","DOI":"10.1063\/1.1591235","article-title":"Shape memory effect in nanoindentation of nickel-titanium thin films","volume":"83","author":"Shaw","year":"2003","journal-title":"Appl. Phys. Lett."},{"doi-asserted-by":"crossref","unstructured":"Jiang, G., and Xie, S. (2019). Comparison of AFM nanoindentation and gold nanoparticle embedding techniques for measuring the properties of polymer thin films. Polymers, 11.","key":"ref_39","DOI":"10.3390\/polym11040617"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1016\/j.porgcoat.2017.09.020","article-title":"Effect of reactive monomers on polymer structure and abrasion resistance of UV cured thin films","volume":"118","author":"Marasinghe","year":"2018","journal-title":"Prog. Org. Coat."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"105685","DOI":"10.1016\/j.porgcoat.2020.105685","article-title":"Preparation of UV curable organic\/inorganic hybrid coatings-a review","volume":"145","author":"Liu","year":"2020","journal-title":"Prog. Org. Coat."},{"doi-asserted-by":"crossref","unstructured":"Hasanain, F.A., and Nassar, H.M. (2021). Utilizing light cure units: A concise narrative review. Polymers, 13.","key":"ref_42","DOI":"10.3390\/polym13101596"},{"doi-asserted-by":"crossref","unstructured":"Czub, P., and Sienkiewicz, A. (2021). Cure reactions of polymer coatings. Polymer Coatings: Technologies and Applications, CRC Press.","key":"ref_43","DOI":"10.1201\/9780429199226-8"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"310","DOI":"10.1002\/pi.4302","article-title":"Controlling the surface wettability of poly(sulfone) films by UV-assisted treatment: Benefits in relation to plasma treatment","volume":"62","author":"Kessler","year":"2013","journal-title":"Polym. Int."},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1762","DOI":"10.1039\/C9MH00217K","article-title":"Chemistries and capabilities of photo-formable and photoreversible crosslinked polymer networks","volume":"6","author":"Hughes","year":"2019","journal-title":"Mater. Horiz."},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"142","DOI":"10.1016\/j.slast.2023.02.003","article-title":"Bioprinting the future using light: A review on photocrosslinking reactions, photoreactive groups, and photoinitiators","volume":"28","author":"Elkhoury","year":"2023","journal-title":"SLAS Technol."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"215307","DOI":"10.1016\/j.ccr.2023.215307","article-title":"Organometallic and coordinative photoresist materials for EUV lithography and related photolytic mechanisms","volume":"493","author":"Lim","year":"2023","journal-title":"Coord. Chem. Rev."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"107039","DOI":"10.1016\/j.porgcoat.2022.107039","article-title":"Low-gloss UV-curable coatings: Light mechanisms, formulations and processes\u2014A review","volume":"171","author":"Calvez","year":"2022","journal-title":"Prog. Org. Coat."},{"doi-asserted-by":"crossref","unstructured":"Ribas-Massonis, A., Cicujano, M., Duran, J., Besalu, E., and Poater, A. (2022). Free-Radical Photopolymerization for Curing Products for Refinish Coatings Market. Polymers, 14.","key":"ref_49","DOI":"10.3390\/polym14142856"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/18\/4413\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T15:57:48Z","timestamp":1760111868000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/29\/18\/4413"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,9,17]]},"references-count":49,"journal-issue":{"issue":"18","published-online":{"date-parts":[[2024,9]]}},"alternative-id":["molecules29184413"],"URL":"https:\/\/doi.org\/10.3390\/molecules29184413","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2024,9,17]]}}}