{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,27]],"date-time":"2026-08-27T02:53:40Z","timestamp":1787799220756,"version":"build-2784847793"},"reference-count":56,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2025,1,24]],"date-time":"2025-01-24T00:00:00Z","timestamp":1737676800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["aces.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2025,2,17]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The extent of conformational change of the porphyrin macrocycle during the course of protonation was observed, both experimentally and theoretically. For synthesised <jats:italic>\u03b2<\/jats:italic>\u2010substituted octaphenylporphyrin (OPP) ring systems, these macrocyclic distortions have been investigated by spectrophotometric titrations, electrochemical, variable temperature nuclear magnetic resonance (VT\u2010NMR) and computational analysis. Protonation\u2010induced non\u2010planarity in a macrocyclic system is experimentally observed in a single step during spectrophotometric titration. The addition of trifluoroacetic acid (TFA) eventually formed dicationic form while tetrabutylammonium hydroxide (TBAOH) was employed for deprotonation study for titration in toluene. The progress of the protonation i.\u2009e. the addition of proton to the core of the ring was monitored by UV\/Vis spectroscopy, which was also determined log\u03b2 value. The spectral changes demonstrate the conformational flexibility of these macrocyclic systems correlating with the photophysical properties. The degree of nonplanarity exhibited incremental progress in response to protonation, with a specific order observed: H<jats:sub>2<\/jats:sub>TPP&lt;H<jats:sub>2<\/jats:sub>OPP&lt;H<jats:sub>2<\/jats:sub>OPPBr<jats:sub>4<\/jats:sub>&lt;H<jats:sub>2<\/jats:sub>OPPBr<jats:sub>3<\/jats:sub>NO<jats:sub>2<\/jats:sub>. VT\u2010NMR experiments were carried out in dichloromethane over a temperature range of 193\u2013298\u2005K, providing dynamic behaviour of these systems. Furthermore, our study delved into the structural aspects, frontier molecular orbitals and ground state energies of H<jats:sub>4<\/jats:sub>P(CF<jats:sub>3<\/jats:sub>COO)<jats:sub>2<\/jats:sub> and absorption bands computed at the TD\u2010B3LYP\/6\u201031G level of theory, anticipated a red shift in both the Soret and Q<jats:sub>0,0<\/jats:sub> bands. This theoretical prediction aligns seamlessly with the experimental findings from spectrophotometric titrations, providing validation to our computation insights. In summary, this comprehensive study elucidates the extent of conformational changes occurring in <jats:italic>\u03b2<\/jats:italic>\u2010substituted octaphenylporphyrin (OPP) ring systems upon protonation and deprotonation.<\/jats:p>","DOI":"10.1002\/asia.202400719","type":"journal-article","created":{"date-parts":[[2024,12,23]],"date-time":"2024-12-23T13:01:22Z","timestamp":1734958882000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Effect of Protonation\u2010Induced Distortions on the Spectral Properties and Electronic Structure of Octaphenylporphyrins through UV\u2010Vis and VT\u2010NMR Spectral, Electrochemical and <i>Ab Initio<\/i> Studies"],"prefix":"10.1002","volume":"20","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-3984-0459","authenticated-orcid":false,"given":"Nivedita","family":"Rana","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Roorkee  Roorkee 247667 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7499-9628","authenticated-orcid":false,"given":"Soni","family":"Kumari","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Roorkee  Roorkee 247667 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6667-3759","authenticated-orcid":false,"given":"Muniappan","family":"Sankar","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Technology Roorkee  Roorkee 247667 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,1,24]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tibs.2006.01.001"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0606144104"},{"key":"e_1_2_7_3_1","first-page":"31","volume":"27","author":"Shelnutt J. A.","year":"1998","journal-title":"J. Chem. Soc."},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0280933"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CC06254C"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1149\/06616.0001ecst"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/j.1460-2075.1989.tb08338.x"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1016\/1011-1344(92)85150-S"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF01902840"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.5b00106"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201801691"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00051a019"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/B511389J"},{"key":"e_1_2_7_14_1","author":"Lavallee D. K.","year":"1987","journal-title":"VCH Publ. New York"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja01013a001"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199424851"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/(SICI)1099-1409(199902)3:2<99::AID-JPP109>3.0.CO;2-6"},{"key":"e_1_2_7_18_1","first-page":"317","author":"Hoard J. L.","year":"1975","journal-title":"Elsevier"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201806281"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201303141"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(95)02405-0"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic970765g"},{"issue":"6","key":"e_1_2_7_23_1","first-page":"90","volume":"16","author":"Rau W. G.","year":"1977","journal-title":"Prog. Nucl. Magn. Reson. Spectrosc."},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00184a019"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1039\/b806282j"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp030999n"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo01288a053"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/ac60325a011"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ac50044a012"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1039\/b414483j"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200601654"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/cm802460t"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/b717958h"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1142\/S1088424609000164"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja806261q"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200802601"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9716214"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp060931i"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja9716214"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201606012"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1142\/S1088424613500557"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5RA20445C"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(84)85009-7"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6RA12520D"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1039\/p29740001136"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.dyepig.2023.111416"},{"issue":"3","key":"e_1_2_7_47_1","first-page":"307","volume":"10","author":"Fleischer E. B.","year":"1963","journal-title":"Rev. Pure, Appl. Chem."},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2sc20271a"},{"key":"e_1_2_7_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cc33668e"},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp001631i"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo0708700"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00210a002"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja00760a056"},{"key":"e_1_2_7_54_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.1c06621"},{"key":"e_1_2_7_55_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022-2852(61)90236-3"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022-2852(63)90011-0"}],"container-title":["Chemistry \u2013 An Asian Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/asia.202400719","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T18:43:48Z","timestamp":1759949028000},"score":1,"resource":{"primary":{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/10.1002\/asia.202400719"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,1,24]]},"references-count":56,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2025,2,17]]}},"alternative-id":["10.1002\/asia.202400719"],"URL":"https:\/\/doi.org\/10.1002\/asia.202400719","archive":["Portico"],"relation":{},"ISSN":["1861-4728","1861-471X"],"issn-type":[{"value":"1861-4728","type":"print"},{"value":"1861-471X","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,1,24]]},"assertion":[{"value":"2024-06-20","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-01-24","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202400719"}}