{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T04:57:28Z","timestamp":1787029048677,"version":"build-2736575974"},"reference-count":37,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2020,10,16]],"date-time":"2020-10-16T00:00:00Z","timestamp":1602806400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"CNPq, FAPEMA, MINECO, EU-FEDER","award":["431943\/2016-8, COOPI-07771\/17, MAT2017-86453-R, ED431G\/09"],"award-info":[{"award-number":["431943\/2016-8, COOPI-07771\/17, MAT2017-86453-R, ED431G\/09"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Temperature-dependent Raman scattering and differential scanning calorimetry were applied to the study of the hybrid organic-inorganic azide-perovskite [(CH3)4N][Cd(N3)3], a compound with multiple structural phase transitions as a function of temperature. A significant entropy variation was observed associated to such phase transitions, |\u2206S| ~ 62.09 J\u00b7kg\u22121 K\u22121, together with both a positive high barocaloric (BC) coefficient |\u03b4Tt\/\u03b4P| ~ 12.39 K kbar\u22121 and an inverse barocaloric (BC) coefficient |\u03b4Tt\/\u03b4P| ~ \u22126.52 kbar\u22121, features that render this compound interesting for barocaloric applications. As for the obtained Raman spectra, they revealed that molecular vibrations associated to the NC4, N3\u2013 and CH3 molecular groups exhibit clear anomalies during the phase transitions, which include splits and discontinuity in the phonon wavenumber and lifetime. Furthermore, variation of the TMA+ and N3\u2013 modes with temperature revealed that while some modes follow the conventional red shift upon heating, others exhibit an unconventional blue shift, a result which was related to the weakening of the intermolecular interactions between the TMA (tetramethylammonium) cations and the azide ligands and the concomitant strengthening of the intramolecular bondings. Therefore, these studies show that Raman spectroscopy is a powerful tool to gain information about phase transitions, structures and intermolecular interactions between the A-cation and the framework, even in complex hybrid organic-inorganic perovskites with highly disordered phases.<\/jats:p>","DOI":"10.3390\/molecules25204754","type":"journal-article","created":{"date-parts":[[2020,10,17]],"date-time":"2020-10-17T08:14:50Z","timestamp":1602922490000},"page":"4754","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["Raman Spectroscopy Studies on the Barocaloric Hybrid Perovskite [(CH3)4N][Cd(N3)3]"],"prefix":"10.3390","volume":"25","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5580-6413","authenticated-orcid":false,"given":"Rosivaldo Xavier","family":"da Silva","sequence":"first","affiliation":[{"name":"Coordena\u00e7\u00e3o de Ci\u00eancias Naturais, Universidade Federal do Maranh\u00e3o, Campus VII, S\u00e3o Lu\u00eds 65400-000, Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Carlos William","family":"de Araujo Paschoal","sequence":"additional","affiliation":[{"name":"Departamento de F\u00edsica, Universidade Federal do Cear\u00e1, Fortaleza 65455-900, Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3156-8673","authenticated-orcid":false,"given":"Clenilton","family":"Costa dos Santos","sequence":"additional","affiliation":[{"name":"Departamento de F\u00edsica, CCET, Universidade Federal do Maranh\u00e3o, S\u00e3o Lu\u00eds 65085-580, Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1671-9979","authenticated-orcid":false,"given":"Alberto","family":"Garc\u00eda-Fern\u00e1ndez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Facultade de Ciencias y CICA, Universidade da Coru\u00f1a, 15071 A Coru\u00f1a, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7991-2819","authenticated-orcid":false,"given":"Jorge","family":"Salgado-Beceiro","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Facultade de Ciencias y CICA, Universidade da Coru\u00f1a, 15071 A Coru\u00f1a, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0117-6855","authenticated-orcid":false,"given":"Mar\u00eda Antonia","family":"Se\u00f1ar\u00eds-Rodr\u00edguez","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Facultade de Ciencias y CICA, Universidade da Coru\u00f1a, 15071 A Coru\u00f1a, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Manuel","family":"Sanchez-Andujar","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Facultade de Ciencias y CICA, Universidade da Coru\u00f1a, 15071 A Coru\u00f1a, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ariel","family":"Nonato Almeida de Abreu Silva","sequence":"additional","affiliation":[{"name":"Coordena\u00e7\u00e3o de Ci\u00eancias Naturais, Universidade Federal do Maranh\u00e3o, Campus do Bacabal, S\u00e3o Lu\u00eds 65700-000, Brazil"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,10,16]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Li, W., Wang, Z., Deschler, F., Gao, S., Friend, R.H., and Cheetham, A.K. 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