{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T03:57:32Z","timestamp":1760241452078,"version":"build-2065373602"},"reference-count":28,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2018,3,2]],"date-time":"2018-03-02T00:00:00Z","timestamp":1519948800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Thermally activated delayed fluorescence (TADF) of 12C70 and 13C70 was observed up to 140 \u00b0C in a p-tert-butyldihomooxacalix[4]arene solid matrix, a temperature range significantly higher than that of previous TADF quantitative studies. An effective singlet\u2013triplet energy gap of 29 kJ\/mol and triplet formation quantum yields of 0.97 and 0.99 were measured for 12C70 and 13C70, respectively. The photophysical properties of the two fullerenes in this new matrix are comparable to those obtained in polystyrene at a lower temperature range. Calixarenes are proposed to be suitable matrices for high temperature TADF studies and applications.<\/jats:p>","DOI":"10.3390\/molecules23030558","type":"journal-article","created":{"date-parts":[[2018,3,2]],"date-time":"2018-03-02T11:53:40Z","timestamp":1519991620000},"page":"558","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Calixarenes as High Temperature Matrices for Thermally Activated Delayed Fluorescence: C70 in Dihomooxacalix[4]arene"],"prefix":"10.3390","volume":"23","author":[{"given":"Tiago","family":"Palmeira","sequence":"first","affiliation":[{"name":"CQFM-IN and IBB\u2014Institute of Bioengineering and Biosciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8727-7077","authenticated-orcid":false,"given":"Alexandre","family":"Miranda","sequence":"additional","affiliation":[{"name":"CQFM-IN and IBB\u2014Institute of Bioengineering and Biosciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal"},{"name":"Centro de Qu\u00edmica Estrutural, Faculdade de Ci\u00eancias da Universidade de Lisboa, Edif\u00edcio C8, 1749-016 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7297-5139","authenticated-orcid":false,"given":"Paula","family":"Marcos","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Faculdade de Ci\u00eancias da Universidade de Lisboa, Edif\u00edcio C8, 1749-016 Lisboa, Portugal"},{"name":"Faculdade de Farm\u00e1cia da Universidade de Lisboa, Av. Prof. Gama Pinto, 1649-003 Lisboa, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2946-1498","authenticated-orcid":false,"given":"M\u00e1rio","family":"Berberan-Santos","sequence":"additional","affiliation":[{"name":"CQFM-IN and IBB\u2014Institute of Bioengineering and Biosciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2018,3,2]]},"reference":[{"key":"ref_1","unstructured":"Valeur, B., and Berberan-Santos, M.N. (2001). Molecular Fluorescence: Principles and Applications, Wiley-VCH. [2nd ed.]. ISBNs 3-527-29919-X (Hardcover), 3-527-60024-8 (Electronic)."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"9391","DOI":"10.1021\/ja961782s","article-title":"Unusually Strong Delayed Fluorescence of C70","volume":"118","author":"Garcia","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"204510","DOI":"10.1063\/1.2734974","article-title":"Thermally activated delayed fluorescence as a cycling process between excited singlet and triplet states: Application to the fullerenes","volume":"126","year":"2007","journal-title":"J. Chem. Phys."},{"key":"ref_4","unstructured":"Zander, M. (1968). Phosphorimetry, Academic Press."},{"key":"ref_5","unstructured":"Parker, C.A. (1968). Photoluminescence of Solutions, Elsevier."},{"key":"ref_6","unstructured":"McGlynn, S.P., Azumi, T., and Kinoshita, M. (1969). Molecular Spectroscopy of the Triplet State, Prentice Hall."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1894","DOI":"10.1039\/tf9615701894","article-title":"Triplet-singlet emission in fluid solutions. Phosphorescence of eosin","volume":"57","author":"Parker","year":"1961","journal-title":"Trans. Faraday Soc."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"438","DOI":"10.1016\/0009-2614(71)80329-9","article-title":"Temperature effects on the intramolecular decay of the lowest triplet state of benzophenone","volume":"10","author":"Jones","year":"1971","journal-title":"Chem. Phys. Lett."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/S0022-2313(99)00019-8","article-title":"Non-monotonic temperature dependence in molecular referenced pressure-sensitive paint (MR-PSP)","volume":"82","author":"Coyle","year":"1999","journal-title":"J. Lumin."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"4264","DOI":"10.1039\/C6SC00542J","article-title":"\u201cRate-limited effect\u201d of reverse intersystem crossing process: The key for tuning thermally activated delayed fluorescence lifetime and efficiency roll-off of organic light emitting diodes","volume":"7","author":"Cai","year":"2016","journal-title":"Chem. Sci."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"701","DOI":"10.1021\/acs.jpcc.6b10554","article-title":"Kinetic Criteria for optimal thermally activited delayed fluorescence in photoluminescence and in electroluminescence","volume":"121","author":"Palmeira","year":"2017","journal-title":"J. Phys. Chem. C"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2317","DOI":"10.1002\/anie.200603754","article-title":"Optical sensing and imaging of trace oxygen with record response","volume":"46","author":"Nagl","year":"2007","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"3643","DOI":"10.1002\/chem.200601580","article-title":"An optical thermometer based on the delayed fluorescence of C70","volume":"13","author":"Nagl","year":"2007","journal-title":"Chem. Eur. J."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"1247","DOI":"10.1002\/cphc.201100156","article-title":"The brightest fullerene: A new isotope effect in molecular fluorescence and phosphorescence","volume":"12","year":"2011","journal-title":"ChemPhysChem"},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1300","DOI":"10.1021\/ac303486f","article-title":"Sensing and imaging of oxygen with parts per billion limits of detection and based on the quenching of the delayed fluorescence of 13C70 fullerene in polymer host","volume":"85","author":"Kochmann","year":"2013","journal-title":"Anal. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"035002","DOI":"10.1088\/2050-6120\/2\/3\/035002","article-title":"Temperature dependence of the phosphorescence and of the thermally activated delayed fluorescence of 12C70 and 13C70 in amorphous polymer matrices. Is a second triplet involved?","volume":"2","author":"Palmeira","year":"2014","journal-title":"Methods Appl. Fluoresc."},{"key":"ref_17","unstructured":"Gutsche, C.D. (2008). Calixarenes: An Introduction, The Royal Society of Chemistry. [2nd ed.]."},{"key":"ref_18","doi-asserted-by":"crossref","unstructured":"Asfari, Z., Bohmer, V., Harrowfield, J., and Vicens, J. (2001). Complexation of Fullerenes. Calixarenes 2001, Kluwer Academic Publishers.","DOI":"10.1007\/0-306-47522-7"},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Neri, P., Sessler, J.L., and Wang, M.-X. (2016). Calixarenes and Fullerenes. Calixarenes and Beyond, Springer International Publishing.","DOI":"10.1007\/978-3-319-31867-7"},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Neri, P., Sessler, J.L., and Wang, M.-X. (2016). Functionalization and Properties of Homooxacalixarenes. Calixarenes and Beyond, Springer International Publishing.","DOI":"10.1007\/978-3-319-31867-7"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"2213","DOI":"10.1016\/S0040-4039(01)93679-2","article-title":"Calixarenes. II. The isolation and characterization of the calix[4]arene and the bishomooxacalix[4]arene from a p-t-butylphenol-formaldehyde condensation product","volume":"20","author":"Gutsche","year":"1979","journal-title":"Tetrahedron Lett."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3782","DOI":"10.1021\/ja00403a028","article-title":"Calixarenes. 4. The synthesis, characterization, and properties of the calixarenes from p-tert-butylphenol","volume":"103","author":"Gutsche","year":"1981","journal-title":"J. Am. Chem. Soc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"965","DOI":"10.1007\/BF01983614","article-title":"The glass transition temperature of polystyrene","volume":"46","author":"Rieger","year":"1996","journal-title":"J. Therm. Anal."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"38008","DOI":"10.1021\/acsami.7b10669","article-title":"Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter","volume":"9","author":"Zach","year":"2017","journal-title":"ACS Appl. Mater. Interfaces"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s10895-005-0049-5","article-title":"A molecular thermometer based on the delayed fluorescence of C70 dispersed in a polystyrene film","volume":"16","year":"2006","journal-title":"J. Fluoresc."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Yersin, H. (2018). TADF kinetics and data analysis in photoluminescence and electroluminescence. Highly Efficient OLEDs: Materials Based on Thermally Activated Delayed Fluorescence, Wiley-VCH.","DOI":"10.1002\/9783527691722"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1007\/BF00707687","article-title":"New synthesis and complexing properties of p-tert-butyldihomooxacalix[4]arene. Structure of its 1:2 complex with tetrahydronfuran","volume":"22","author":"Bavoux","year":"1995","journal-title":"J. Incl. Phenom."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"015002","DOI":"10.1088\/2050-6120\/1\/1\/015002","article-title":"Methods for the analysis of complex fluorescence decays: Sum of Becquerel functions versus sum of exponentials","volume":"1","author":"Menezes","year":"2013","journal-title":"Methods Appl. Fluoresc."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/23\/3\/558\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T14:57:17Z","timestamp":1760194637000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/23\/3\/558"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2018,3,2]]},"references-count":28,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2018,3]]}},"alternative-id":["molecules23030558"],"URL":"https:\/\/doi.org\/10.3390\/molecules23030558","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2018,3,2]]}}}