{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T16:25:04Z","timestamp":1786465504377,"version":"build-2736575974"},"reference-count":43,"publisher":"American Chemical Society (ACS)","issue":"31","license":[{"start":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T00:00:00Z","timestamp":1785110400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100003725","name":"National Research Foundation of Korea","doi-asserted-by":"publisher","award":["RS-2023-NR076953"],"award-info":[{"award-number":["RS-2023-NR076953"]}],"id":[{"id":"10.13039\/501100003725","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003725","name":"National Research Foundation of Korea","doi-asserted-by":"publisher","award":["RS-2024-00348644"],"award-info":[{"award-number":["RS-2024-00348644"]}],"id":[{"id":"10.13039\/501100003725","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003725","name":"National Research Foundation of Korea","doi-asserted-by":"publisher","award":["RS-2025-24523484"],"award-info":[{"award-number":["RS-2025-24523484"]}],"id":[{"id":"10.13039\/501100003725","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003725","name":"National Research Foundation of Korea","doi-asserted-by":"publisher","award":["RS-2025-25408880"],"award-info":[{"award-number":["RS-2025-25408880"]}],"id":[{"id":"10.13039\/501100003725","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,11]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The preparation and characterization of volatile cis\/trans stereoisomers require controlled access to defined isomeric forms and independent validation of their molecular compositions under spectroscopic conditions. Here, we report the integrated synthetic-spectroscopic characterization of trans-3-penten-1-yne, a volatile C5H6 enyne stereoisomer. A stereochemistry-preserving preparation route using trans-crotonaldehyde, combined with Corey-Fuchs-type dibromoolefin formation, a trimethylsilyl-protected enyne intermediate, mild deprotection, and freeze distillation, enables the low-temperature isolation of a trans-enriched sample while minimizing evaporative loss. The isomeric composition is first determined via nuclear magnetic resonance (NMR) spectroscopy and then independently evaluated under jet-cooled gas-phase conditions using vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. The good consistency between the NMR- and VUV-MATI-derived trans\/cis ratios indicates that the trans-enrichment of the isolated sample is retained during vaporization and supersonic expansion. The VUV-MATI spectrum yields the precise adiabatic ionization energy of the trans-isomer and enables the differentiation of its threshold features from those of the residual cis-component. Infrared-dip VUV-MATI spectroscopy, supported by anharmonic simulation, confirms the neutral-state vibrational fingerprint of trans-3-penten-1-yne, and Franck\u2013Condon analysis reveals that the cationic vibronic structure is consistent with the ionization of the well-defined trans neutral precursor. This combined approach establishes VUV-MATI spectroscopy as a gas-phase analytical complement to NMR spectroscopy in analyzing volatile stereoisomeric hydrocarbons and provides a reliable framework for interpreting the congested ionization spectra of labile enyne systems.<\/jats:p>","DOI":"10.1021\/acsomega.6c06696","type":"journal-article","created":{"date-parts":[[2026,7,27]],"date-time":"2026-07-27T08:09:42Z","timestamp":1785139782000},"page":"47071-47082","source":"Crossref","is-referenced-by-count":0,"title":["Stereodefined Precursor-Based Preparation and Isomer-Resolved\nSpectroscopic Validation of\n                    <i>trans<\/i>\n                    -3-Penten-1-yne"],"prefix":"10.1021","volume":"11","author":[{"given":"Sung Man","family":"Park","sequence":"first","affiliation":[{"name":"Kangwon National University , , ,","place":["Chuncheon, Republic of Korea, 24341"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"So Yeon","family":"Kim","sequence":"additional","affiliation":[{"name":"Kangwon National University , , ,","place":["Chuncheon, Republic of Korea, 24341"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4989-2831","authenticated-orcid":true,"given":"Wonchul","family":"Lee","sequence":"additional","affiliation":[{"name":"Kangwon National University , , ,","place":["Chuncheon, Republic of Korea, 24341"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4440-6240","authenticated-orcid":true,"given":"Chan Ho","family":"Kwon","sequence":"additional","affiliation":[{"name":"Kangwon National University , , ,","place":["Chuncheon, Republic of Korea, 24341"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,27]]},"reference":[{"key":"2026081110140501900_cit1","doi-asserted-by":"publisher","first-page":"3199","DOI":"10.1021\/ol026266n","article-title":"One-Pot Synthesis\nof Symmetrical and Unsymmetrical Bisarylethynes by a Modification\nof the Sonogashira Coupling Reaction","volume":"4","author":"Mio","year":"2002","journal-title":"Org. Lett."},{"key":"2026081110140501900_cit2","doi-asserted-by":"publisher","first-page":"4376","DOI":"10.1021\/jp0569685","article-title":"Identification\nof C5Hx Isomers in Fuel-Rich Flames by Photoionization\nMass Spectrometry and Electronic Structure Calculations","volume":"110","author":"Hansen","year":"2006","journal-title":"J. Phys. Chem. A"},{"key":"2026081110140501900_cit3","doi-asserted-by":"publisher","first-page":"5093","DOI":"10.1021\/jp403637t","article-title":"Reaction\nRate and Isomer-Specific Product Branching Ratios of C2H + C4H8: 1-Butene, Cis-2-Butene, Trans-2-Butene,\nand Isobutene at 79 K","volume":"117","author":"Bouwman","year":"2013","journal-title":"J. Phys. Chem. A"},{"key":"2026081110140501900_cit4","doi-asserted-by":"publisher","first-page":"6241","DOI":"10.1021\/ac5018343","article-title":"Vacuum Ultraviolet Detection for\nGas Chromatography","volume":"86","author":"Schug","year":"2014","journal-title":"Anal. Chem."},{"key":"2026081110140501900_cit5","doi-asserted-by":"publisher","first-page":"4486","DOI":"10.1021\/acs.orglett.5b02149","article-title":"From Stereodefined\nCyclobutenes to Dienes: Total Syntheses of Ieodomycin D and the Southern\nFragment of Macrolactin A","volume":"17","author":"Souris","year":"2015","journal-title":"Org. Lett."},{"key":"2026081110140501900_cit6","doi-asserted-by":"publisher","first-page":"20090","DOI":"10.1021\/jacs.2c09360","article-title":"A General Stereoselective\nSynthesis\nof Dendralenes","volume":"144","author":"Fan","year":"2022","journal-title":"J. Am. Chem. Soc."},{"key":"2026081110140501900_cit7","doi-asserted-by":"publisher","first-page":"2759","DOI":"10.1002\/chem.200305543","article-title":"Total Synthesis and Biological Evaluation\nof the Protein\nPhosphatase 2A Inhibitor Cytostatin and Analogues","volume":"10","author":"Bialy","year":"2004","journal-title":"Chem.\u2500Eur. J."},{"key":"2026081110140501900_cit8","doi-asserted-by":"publisher","first-page":"9378","DOI":"10.1021\/acs.joc.9b01307","article-title":"CsF-Mediated In-situ Desilylation\nof TMS-Alkynes for Sonogashira Reaction","volume":"84","author":"Capani","year":"2019","journal-title":"J.\nOrg. Chem."},{"key":"2026081110140501900_cit9","doi-asserted-by":"publisher","first-page":"3110","DOI":"10.1063\/1.1676554","article-title":"Microwave\nSpectrum, Barrier to Internal Rotation, and\nDipole Moment of Cis-3-Penten-1-Yne","volume":"55","author":"Ford","year":"1971","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit10","doi-asserted-by":"publisher","first-page":"344","DOI":"10.1016\/0022-2852(72)90090-2","article-title":"The Microwave Spectrum, Barrier to Internal Rotation,\nand Dipole Moment of Trans-3-Penten-1-Yne","volume":"42","author":"Ford","year":"1972","journal-title":"J. Mol. Spectrosc."},{"key":"2026081110140501900_cit11","doi-asserted-by":"publisher","first-page":"3907","DOI":"10.1021\/jp301015b","article-title":"Bimolecular\nRate\nConstant and Product Branching Ratio measurements for the Reaction\nof C2H with Ethene and Propene at 79 K","volume":"116","author":"Bouwman","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"2026081110140501900_cit12","doi-asserted-by":"publisher","first-page":"280","DOI":"10.1021\/acs.jpca.7b10382","article-title":"Synchrotron\nPhotoionization Study\nof Furan and 2-Methylfuran Reactions with Methylidyne Radical (CH)\nat 298 K","volume":"122","author":"Carrasco","year":"2018","journal-title":"J. Phys. Chem. A"},{"key":"2026081110140501900_cit13","doi-asserted-by":"publisher","first-page":"852","DOI":"10.1086\/319009","article-title":"The Formation of\nC5H6 Isomers as Potential Key Intermediates\nto Polycyclic Aromatic Hydrocarbon-Like Molecules","volume":"548","author":"Kaiser","year":"2001","journal-title":"Astrophys. J."},{"key":"2026081110140501900_cit14","doi-asserted-by":"publisher","first-page":"1599","DOI":"10.1007\/s00214-014-1599-x","article-title":"Theoretical and\nKinetic Study of Reaction C2H + C3H6 on the C5H7 Potential Energy Surface","volume":"134","author":"Gong","year":"2015","journal-title":"Theor. Chem. Acc."},{"key":"2026081110140501900_cit15","doi-asserted-by":"publisher","first-page":"13226","DOI":"10.1039\/c8ra01449c","article-title":"Formation\nof bicyclic polycyclic aromatic hydrocarbons (PAHs) from the reaction\nof a phenyl radical with cis-3-penten-1-yne","volume":"8","author":"Wei","year":"2018","journal-title":"RSC Adv."},{"key":"2026081110140501900_cit16","doi-asserted-by":"publisher","first-page":"1889","DOI":"10.1021\/acs.jpca.2c00297","article-title":"Gas-Phase\nStudy of the Elementary Reaction of the D1-ethynyl\nRadical (C2D; X2\u03a3+) with Propylene\n(C3H6; X1A\u2032) under Single\nCollision Conditions","volume":"126","author":"Goettl","year":"2022","journal-title":"J. Phys. Chem. A"},{"key":"2026081110140501900_cit17","doi-asserted-by":"publisher","first-page":"4934","DOI":"10.1039\/D4CP03728F","article-title":"Formation\nof C5H6 Isomers: A Combination of Experimental\nand Computational Investigation","volume":"27","author":"Zhang","year":"2025","journal-title":"Phys. Chem.\nChem. Phys."},{"key":"2026081110140501900_cit18","doi-asserted-by":"publisher","first-page":"174303","DOI":"10.1063\/1.4900569","article-title":"One-photon mass-analyzed\nthreshold ionization (MATI) spectroscopy of pyridine: Determination\nof accurate ionization energy and cationic structure","volume":"141","author":"Lee","year":"2014","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit19","doi-asserted-by":"publisher","first-page":"014304","DOI":"10.1063\/1.5110436","article-title":"Formyl\ntorsion and cationic structure of gauche conformer\nin isobutanal by conformer-specific VUV-MATI spectroscopy and Franck-Condon\nfitting","volume":"151","author":"Lee","year":"2019","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit20","doi-asserted-by":"publisher","first-page":"28383","DOI":"10.1039\/D0CP05782G","article-title":"Conformer-specific\nVUV-MATI spectroscopy of methyl vinyl ketone: Stabilities and cationic\nstructures of the s-trans and s-cis conformers","volume":"22","author":"Park","year":"2020","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026081110140501900_cit21","doi-asserted-by":"publisher","first-page":"9472","DOI":"10.1021\/acs.jpclett.3c02280","article-title":"Unraveling the conformational preference of morpholine:\nInsights from infrared resonant vacuum ultraviolet photoionization\nmass spectroscopy","volume":"14","author":"Park","year":"2023","journal-title":"J. Phys. Chem. Lett."},{"key":"2026081110140501900_cit22","doi-asserted-by":"publisher","first-page":"114308","DOI":"10.1063\/5.0186570","article-title":"Deciphering the\nconformational preference and ionization\ndynamics of tetrahydrofuran: Insight from advanced spectroscopic techniques","volume":"160","author":"Park","year":"2024","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit23","doi-asserted-by":"publisher","first-page":"25949","DOI":"10.1039\/D5CP03603H","article-title":"Resolving s-trans-dominant\nIonization Dynamics in Tiglic\nAldehyde Using VUV-MATI Spectroscopy and PES Analysis","volume":"27","author":"Park","year":"2025","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026081110140501900_cit24","doi-asserted-by":"publisher","first-page":"729","DOI":"10.1021\/acsphyschemau.5c00088","article-title":"Unraveling the Conformational and Electronic Landscape\nof 3-Pyridinecarboxaldehyde: A Spectroscopic Journey Through Conformer-Specific\nIonization","volume":"5","author":"Park","year":"2025","journal-title":"ACS Phys. Chem. Au"},{"key":"2026081110140501900_cit25","doi-asserted-by":"publisher","first-page":"9251","DOI":"10.1021\/acs.jpca.1c07162","article-title":"Development and\nVerification of Conformer-Specific\nVibrational Spectroscopy","volume":"125","author":"Park","year":"2021","journal-title":"J. Phys. Chem. A"},{"key":"2026081110140501900_cit26","doi-asserted-by":"publisher","first-page":"38240","DOI":"10.1039\/D1RA07397D","article-title":"Identification of\nIndividual Conformers in C4H6O isomers using\nConformer-Specific Vibrational Spectroscopy","volume":"11","author":"Park","year":"2021","journal-title":"RSC Adv."},{"issue":"18","key":"2026081110140501900_cit27","doi-asserted-by":"publisher","first-page":"184303","DOI":"10.1063\/5.0331143","article-title":"Isomer-Resolved\nIR\u2013VUV\u2013MATI Spectroscopy of cis-3-Penten-1-yne:\nAdiabatic Ionization Energy and Vibronic Structure","volume":"164","author":"Park","year":"2026","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit28","doi-asserted-by":"publisher","first-page":"6192","DOI":"10.1021\/ol202601s","article-title":"Dialkylaluminum Hydride-Promoted\nCyclodimerization of Silylated 1,3-Enynes via Skeletal Rearrangement","volume":"13","author":"Kinoshita","year":"2011","journal-title":"Org. Lett."},{"key":"2026081110140501900_cit29","doi-asserted-by":"publisher","first-page":"3769","DOI":"10.1016\/S0040-4039(01)94157-7","article-title":"A Synthetic Method for Formyl \u2192 Ethynyl Conversion\n(RCHO \u2192 RC\u2261CH or RC\u2261CR\u2032)","volume":"13","author":"Corey","year":"1972","journal-title":"Tetrahedron Lett."},{"key":"2026081110140501900_cit30","doi-asserted-by":"publisher","first-page":"250","DOI":"10.1007\/BF01341712","article-title":"U\u0308ber\nden Ramaneffekt des Kohlendioxyds","volume":"71","author":"Fermi","year":"1931","journal-title":"Z. Phys."},{"key":"2026081110140501900_cit31","doi-asserted-by":"publisher","first-page":"014108","DOI":"10.1063\/1.1824881","article-title":"Anharmonic\nVibrational Properties by a Full Automated Second-Order Perturbative\nApproach","volume":"122","author":"Barone","year":"2005","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit32","doi-asserted-by":"publisher","first-page":"164203","DOI":"10.1063\/5.0066348","article-title":"Innovative Mass\nSpectrometer for High-Resolution Ion\nSpectroscopy","volume":"155","author":"Lee","year":"2021","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit33","doi-asserted-by":"publisher","first-page":"636","DOI":"10.1002\/bkcs.12508","article-title":"Determination of\nHighest Occupied Molecular Orbital\nand Cationic Structures of Cyclopentanone Using High-Resolution Vacuum\nUltraviolet Mass-Analyzed Threshold Ionization Mass Spectrometry","volume":"43","author":"Lee","year":"2022","journal-title":"Bull. Korean Chem. Soc."},{"key":"2026081110140501900_cit34","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1063\/1.2227036","article-title":"Energy\nLevels and Observed Spectral Lines of Krypton, Kr I Through Kr XXXVI","volume":"36","author":"Saloman","year":"2007","journal-title":"J. Phys. Chem. Ref. Data"},{"key":"2026081110140501900_cist35","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.; Nakatsuji, H.; et al.; .  Gaussian\n16 Rev. C.01; Gaussian Inc.: Wallingford CT, 2016."},{"key":"2026081110140501900_cit36","doi-asserted-by":"publisher","first-page":"5648","DOI":"10.1063\/1.464913","article-title":"Density-Functional\nThermochemistry. III. The Role of Exact Exchange","volume":"98","author":"Becke","year":"1993","journal-title":"J. Chem. Phys."},{"key":"2026081110140501900_cit37","doi-asserted-by":"publisher","first-page":"51","DOI":"10.1016\/j.cplett.2004.06.011","article-title":"A New Hybrid Exchange-Correlation\nFunctional Using the Coulomb Attenuating Method (CAM-B3LYP)","volume":"393","author":"Yanai","year":"2004","journal-title":"Chem. Phys. Lett."},{"key":"2026081110140501900_cit38","doi-asserted-by":"publisher","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 Suite of Density Functionals\nfor Main Group\nThermochemistry, Thermochemical Kinetics, Noncovalent Interactions,\nExcited States, and Transition Elements: Two New Functionals and Systematic\nTesting of Four M06-Class Functionals and 12 Other Functionals","volume":"120","author":"Zhao","year":"2008","journal-title":"Theor. Chem. Acc."},{"key":"2026081110140501900_cit39","doi-asserted-by":"publisher","first-page":"6615","DOI":"10.1039\/b810189b","article-title":"Long-Range Corrected Hybrid Density\nFunctionals with\nDamped Atom-Atom Dispersion Corrections","volume":"10","author":"Chai","year":"2008","journal-title":"Phys.\nChem. Chem. Phys."},{"key":"2026081110140501900_cit40","doi-asserted-by":"publisher","first-page":"618","DOI":"10.1103\/PhysRev.46.618","article-title":"Note on an Approximation Treatment for Many-Electron\nSystems","volume":"46","author":"M\u00f8ller","year":"1934","journal-title":"Phys. Rev."},{"key":"2026081110140501900_cit41","doi-asserted-by":"publisher","first-page":"1910","DOI":"10.1063\/1.443164","article-title":"A Full Coupled-Cluster\nSingles and Doubles Model: The\nInclusion of Disconnected Triples","volume":"76","author":"Purvis","year":"1982","journal-title":"J. Chem.\nPhys."},{"key":"2026081110140501900_cit42","doi-asserted-by":"publisher","first-page":"2687","DOI":"10.1021\/ct900260g","article-title":"Unrestricted\nCoupled Cluster and Brueckner Doubles Variations of W1 Theory","volume":"5","author":"Barnes","year":"2009","journal-title":"J. Chem. Theory Comput."},{"key":"2026081110140501900_cit43","doi-asserted-by":"publisher","first-page":"3453","DOI":"10.1063\/1.1725748","article-title":"Franck-Condon Factors for Polyatomic Molecules","volume":"41","author":"Sharp","year":"1964","journal-title":"J. Chem. Phys."}],"container-title":["ACS Omega"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acsomega.6c06696","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/31\/47071\/66276162\/acsomega.6c06696.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/acsodf\/article-pdf\/11\/31\/47071\/66276162\/acsomega.6c06696.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,8,11]],"date-time":"2026-08-11T15:01:41Z","timestamp":1786460501000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/acsodf\/article\/11\/31\/47071\/5233710\/Stereodefined-Precursor-Based-Preparation-and"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,27]]},"references-count":43,"journal-issue":{"issue":"31","published-online":{"date-parts":[[2026,7,27]]},"published-print":{"date-parts":[[2026,8,11]]}},"URL":"https:\/\/doi.org\/10.1021\/acsomega.6c06696","relation":{},"ISSN":["2470-1343"],"issn-type":[{"value":"2470-1343","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,27]]}}}