{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,12]],"date-time":"2026-01-12T23:37:26Z","timestamp":1768261046768,"version":"3.49.0"},"reference-count":37,"publisher":"MDPI AG","issue":"4","license":[{"start":{"date-parts":[[2022,2,14]],"date-time":"2022-02-14T00:00:00Z","timestamp":1644796800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100005643","name":"University of \u0141\u00f3d\u017a","doi-asserted-by":"publisher","award":["14\/IDUB\/DOS\/2021"],"award-info":[{"award-number":["14\/IDUB\/DOS\/2021"]}],"id":[{"id":"10.13039\/501100005643","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The triflic-acid-promoted cyclization of 1-phenyl-3-(pyren-1-yl)-1H-pyrazole-4-carbaldehyde afforded a mixture of 9-phenyl-7,9-dihydropyreno (10,1-fg)indazole and 9-phenylpyreno(10,1-fg)indazole-7(9H)-one, readily separable by column chromatography. Both products contained a rigid six-ringed pyrazoolympicene backbone and exhibited bright fluorescence in chloroform solution and a weak fluorescence in the solid state. DFT and TD DFT calculations revealed that the lowest excited state (S1) of these compounds is populated via HOMO \u2192LUMO \u03c0-\u03c0 * transition. Furthermore, the synthesized compounds behaved as weak bases and their emission spectra showed substantial changes upon protonation. Therefore, they may be of interest for sensing of strongly acidic fluorophore environments.<\/jats:p>","DOI":"10.3390\/molecules27041272","type":"journal-article","created":{"date-parts":[[2022,2,14]],"date-time":"2022-02-14T20:58:03Z","timestamp":1644872283000},"page":"1272","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Highly Fluorescent Dyes Containing Conformationally Restrained Pyrazolylpyrene (Pyrazoolympicene) Chromophore"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6930-6989","authenticated-orcid":false,"given":"Anna","family":"Wrona-Piotrowicz","sequence":"first","affiliation":[{"name":"Department of Organic Chemistry, Faculty of Chemistry, University of Lodz, Tamka 12, 91-403 Lodz, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9357-2670","authenticated-orcid":false,"given":"Anna","family":"Makal","sequence":"additional","affiliation":[{"name":"Biological and Chemical Research Center, Faculty of Chemistry, University of Warsaw, \u017bwirki i Wigury 101, 02-089 Warsaw, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3403-1126","authenticated-orcid":false,"given":"Janusz","family":"Zakrzewski","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry, Faculty of Chemistry, University of Lodz, Tamka 12, 91-403 Lodz, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,2,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"587","DOI":"10.1021\/cr00018a001","article-title":"Photophysics of preassociated pyrenes in aqueous polymer solutions and in other organized media","volume":"93","author":"Winnik","year":"1993","journal-title":"Chem. Rev."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"17","DOI":"10.1016\/j.cplett.2015.08.070","article-title":"Theoretical calculation of the pyrene emission properties in different solvents","volume":"639","author":"Aschi","year":"2015","journal-title":"Chem. Phys. Lett."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"762","DOI":"10.1039\/C9QM00090A","article-title":"Pyrene-based aggregation-induced emission luminogens and their applications","volume":"3","author":"Islam","year":"2019","journal-title":"Mater. Chem. Front."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"6527","DOI":"10.1021\/la2047646","article-title":"New Insights in the Study of Pyrene Excimer Fluorescence to Characterize Macromolecules and their Supramolecular Assemblies in Solution","volume":"28","author":"Duhamel","year":"2012","journal-title":"Langmuir"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"964","DOI":"10.1002\/asia.201000724","article-title":"Supramolecular Chemical Sensors Based on Pyrene Monomer\u2013Excimer Dual Luminescence","volume":"6","author":"Karuppannan","year":"2011","journal-title":"Chem. Asian J."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"108102","DOI":"10.1016\/j.dyepig.2019.108102","article-title":"An intermolecular pyrene excimer-based ratiometric fluorescent probes for extremely acidic pH and its applications","volume":"174","author":"Liu","year":"2020","journal-title":"Dyes Pigm."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"7260","DOI":"10.1021\/cr100428a","article-title":"Pyrene-Based Materials for Organic Electronics","volume":"111","year":"2011","journal-title":"Chem. Rev."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"11898","DOI":"10.1002\/chem.201600465","article-title":"Functionalization of Pyrene To Prepare Luminescent Materials-Typical Examples of Synthetic Methodology","volume":"22","author":"Feng","year":"2016","journal-title":"Chem. Eur. J."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"212","DOI":"10.1039\/C3OB41993B","article-title":"Synthesis of substituted pyrenes by indirect methods","volume":"12","author":"Howgego","year":"2014","journal-title":"Org. Biomol. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"3143","DOI":"10.1039\/D0CS00424C","article-title":"Pyrene-based metal organic frameworks: From synthesis to applications","volume":"50","author":"Kinik","year":"2021","journal-title":"Chem. Soc. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1638","DOI":"10.1002\/cphc.202100294","article-title":"Multi-Directional Mechanofluorochromism of Acetyl Pyrenes and Pyrenyl Ynones","volume":"22","author":"Hirai","year":"2021","journal-title":"ChemPhysChem"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"7909","DOI":"10.3390\/molecules16097909","article-title":"Pyrene: A Probe to Study Protein Conformation and Conformational Changes","volume":"16","author":"Bains","year":"2011","journal-title":"Molecules"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"10997","DOI":"10.1039\/D1NJ00158B","article-title":"Pyrene based materials as fluorescent probes in chemical and biological fields","volume":"45","author":"Ayyavoo","year":"2021","journal-title":"New J. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","unstructured":"Krasheninina, O.A., Novopashina, D.S., Apartsin, E.K., and Venyaminova, A.G. (2017). Recent Advances in Nucleic Acid Targeting Probes and Supramolecular Constructs Based on Pyrene-Modified Oligonucleotides. Molecules, 22.","DOI":"10.3390\/molecules22122108"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"19693","DOI":"10.1039\/D0RA02394A","article-title":"Recent progress in chemosensors based on pyrazole derivatives","volume":"10","author":"Tigreros","year":"2020","journal-title":"RSC Adv."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2082","DOI":"10.1021\/ol2004947","article-title":"Rapid One-Pot, Four-Step Synthesis of Highly Fluorescent 1,3,4,5-Tetrasubstituted Pyrazoles","volume":"13","author":"Willy","year":"2011","journal-title":"Org. Lett."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"4157","DOI":"10.1002\/ejoc.200800444","article-title":"Regioselective Three-Component Synthesis of Highly Fluorescent 1,3,5-Trisubstituted Pyrazoles","volume":"2008","author":"Willy","year":"2008","journal-title":"Eur. J. Org. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"17148","DOI":"10.1039\/C5CC05973A","article-title":"AIEE phenomenon: Tetraaryl vs. triaryl pyrazoles","volume":"51","author":"Mukherjee","year":"2015","journal-title":"Chem. Comm."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"10328","DOI":"10.1021\/acs.joc.6b01326","article-title":"One-Pot Coupling\u2013Coupling\u2013Cyclocondensation Synthesis of Fluorescent Pyrazoles","volume":"81","author":"Hoppe","year":"2016","journal-title":"J. Org. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"121664","DOI":"10.1016\/j.jorganchem.2020.121664","article-title":"Synthesis, characterization and fluorescent properties of ferrocenyl pyrazole and triazole ligands and their palladium complexes","volume":"935","author":"Amoah","year":"2021","journal-title":"J. Organomet. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1039\/c6pp00009f","article-title":"Synthesis, regioselective aerobic Pd(II)-catalyzed C\u2013H bond alkenylation and the photophysical properties of pyrenylphenylpyrazoles","volume":"15","author":"Flamholc","year":"2016","journal-title":"Photochem. Photobiol. Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"52","DOI":"10.1016\/j.dyepig.2018.01.047","article-title":"Pyrenylpyrazole-based donor\/acceptor fluorescent dyes: Synthesis and photophysical properties","volume":"154","author":"Flamholc","year":"2018","journal-title":"Dye. Pigm."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"5907","DOI":"10.1021\/acs.joc.0c00236","article-title":"Impact of Cyanine Conformational Restraint in the Near-Infrared Range","volume":"85","author":"Matikonda","year":"2020","journal-title":"J. Org. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"11427","DOI":"10.1021\/acs.analchem.7b02538","article-title":"Rational Engineering of Bioinspired Anthocyanidin Fluorophores with Excellent Two-Photon Properties for Sensing and Imaging","volume":"89","author":"Ren","year":"2017","journal-title":"Anal. Chem."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1887","DOI":"10.1039\/C9CC09064A","article-title":"Conformationally rigid pyrazoloquinazoline \u03b1-amino acids: One- and two-photon induced fluorescence","volume":"56","author":"Bell","year":"2020","journal-title":"Chem. Commun."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"2931","DOI":"10.1016\/j.tetlet.2005.02.152","article-title":"Superacid-promoted reactions of pyrazolecarboxaldehydes and the role of dicationic electrophiles","volume":"46","author":"Klumpp","year":"2005","journal-title":"Tetrahedron Lett."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2011","DOI":"10.1002\/chem.201404877","article-title":"The Synthesis and STM\/AFM Imaging of \u2018Olympicene\u2019 Benzo[cd]pyrenes","volume":"21","author":"Mistry","year":"2015","journal-title":"Chem. Eur. J."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"11","DOI":"10.1016\/j.comptc.2015.01.001","article-title":"Effects of substituent groups and solvent media on Pyrene in ground and excited states: A DFT and TDDFT study","volume":"1056","author":"Acar","year":"2015","journal-title":"Comput. Theor. Chem."},{"key":"ref_29","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_30","doi-asserted-by":"crossref","first-page":"669","DOI":"10.1002\/(SICI)1099-1395(199709)10:9<669::AID-POC933>3.0.CO;2-3","article-title":"Basicity of azoles: Complexes of diiodine with imidazoles, pyrazoles and triazoles","volume":"10","author":"Mokhlisse","year":"1997","journal-title":"J. Phys. Org. Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2861","DOI":"10.1039\/C4NJ02201G","article-title":"A theoretical study of the gas phase (proton affinity) and aqueous (pKa) basicity of a series of 150 pyrazoles","volume":"39","author":"Alkorta","year":"2015","journal-title":"New J. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"4325","DOI":"10.1016\/j.tetlet.2014.06.021","article-title":"The Hammett acidity function H0 in trifluoroacetic acid\u2013dichloromethane mixtures","volume":"55","author":"Suslova","year":"2014","journal-title":"Tetrahedron Lett."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"654","DOI":"10.1111\/php.12326","article-title":"A New Series of Fluorescent Indicators for Super Acids","volume":"91","author":"Shih","year":"2015","journal-title":"Photochem. Photobiol."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2213","DOI":"10.1351\/PAC-REP-10-09-31","article-title":"Standards for photoluminescence quantum yield measurements in solution (IUPAC Technical Report)","volume":"83","author":"Brouwer","year":"2011","journal-title":"Pure Appl. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1107\/S0108767307043930","article-title":"A short history of SHELX","volume":"A64","author":"Sheldrick","year":"2008","journal-title":"Acta Cryst."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1107\/S0021889808042726","article-title":"OLEX2: A complete structure solution, refinement and analysis program","volume":"42","author":"Dolomanov","year":"2009","journal-title":"J. Appl. Cryst."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"453","DOI":"10.1107\/S002188980600731X","article-title":"Mercury: Visualization and analysis of crystal structures","volume":"39","author":"Macrae","year":"2006","journal-title":"J. Appl. Cryst."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/4\/1272\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T22:19:16Z","timestamp":1760134756000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/4\/1272"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,2,14]]},"references-count":37,"journal-issue":{"issue":"4","published-online":{"date-parts":[[2022,2]]}},"alternative-id":["molecules27041272"],"URL":"https:\/\/doi.org\/10.3390\/molecules27041272","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,2,14]]}}}