{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T00:51:27Z","timestamp":1760143887193,"version":"build-2065373602"},"reference-count":24,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2024,3,6]],"date-time":"2024-03-06T00:00:00Z","timestamp":1709683200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001691","name":"JSPS KAKENHI Grant-in-Aid for Scientific Research (C)","doi-asserted-by":"publisher","award":["JP21K05212","JPMXS0421800223"],"award-info":[{"award-number":["JP21K05212","JPMXS0421800223"]}],"id":[{"id":"10.13039\/501100001691","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Iketani Science and Technology Foundation","award":["JP21K05212","JPMXS0421800223"],"award-info":[{"award-number":["JP21K05212","JPMXS0421800223"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Symmetry"],"abstract":"<jats:p>Solution-state photoluminescence (PL) is affected by the electronic state; however, solid-state PL varies widely depending on the aggregated state. Although the synthesis and photophysical properties of unsymmetrical and C3-symmetrical hexaarylbenzenes (HABs) have been reported, the influence of their terminal alkoxy chains on their physical properties remains unclear. Therefore, we synthesized a series of unsymmetrical and C3-symmetrical partially fluorinated HABs with different alkoxy chains and investigated the effects of alkoxy chain length on the thermophysical and photophysical properties. While investigating phase transition behavior, the ethoxy-substituted unsymmetrical derivative revealed a columnar liquid-crystalline phase, whereas the other derivatives only exhibited a phase transition between crystalline and isotropic phases. While evaluating PL behavior, both the unsymmetrical and C3-symmetrical analogs exhibited relatively strong blue PL, independent of the alkoxy chain length. Through-space \u03c0-conjugation caused the PL spectra of C3-symmetrical derivatives to redshift compared to those of unsymmetrical derivatives. Partially fluorinated HABs exhibited relatively strong fluorescence, even in the crystalline state, depending on the alkoxy chain length, owing to the formation of various aggregated structures. Crystalline fluorinated HABs exhibited photochromism, resulting in the appearance of long-wavelength PL bands when exposed to ultraviolet (UV) irradiation, making them promising candidates for PL sensing materials for UV detection.<\/jats:p>","DOI":"10.3390\/sym16030314","type":"journal-article","created":{"date-parts":[[2024,3,6]],"date-time":"2024-03-06T08:43:14Z","timestamp":1709714594000},"page":"314","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Unsymmetrical and C3-Symmetrical Partially Fluorinated Hexaarylbenzenes: Effect of Terminal Alkoxy Chain Length on Photophysical and Thermophysical Behavior"],"prefix":"10.3390","volume":"16","author":[{"given":"Yizhou","family":"Wang","sequence":"first","affiliation":[{"name":"Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6379-0447","authenticated-orcid":false,"given":"Shigeyuki","family":"Yamada","sequence":"additional","affiliation":[{"name":"Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9324-3463","authenticated-orcid":false,"given":"Motohiro","family":"Yasui","sequence":"additional","affiliation":[{"name":"Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tsutomu","family":"Konno","sequence":"additional","affiliation":[{"name":"Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2024,3,6]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"7160","DOI":"10.1021\/acs.chemmater.1c02460","article-title":"Dual-state emission (DSE) in organic fluorophores: Design and applications","volume":"33","year":"2021","journal-title":"Chem. Mater."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"101596","DOI":"10.1016\/j.mtchem.2023.101596","article-title":"Dual-state emission: The compatible art of substantial rigidity and twisting conformation within a single molecule","volume":"30","author":"Xia","year":"2023","journal-title":"Mater. Today Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"2921","DOI":"10.1021\/acs.jpcb.2c01387","article-title":"Alkyl-engineered dual-state luminogens with pronounced odd-even effects: Quantum yields with up to 48% difference and crystallochromy with up to 22 nm difference","volume":"126","author":"Yin","year":"2022","journal-title":"J. Phys. Chem. B"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"119529","DOI":"10.1016\/j.jlumin.2022.119529","article-title":"Achieving dual-state emission and high-contrast mechanochromic luminescence based on donor-acceptor type phenothiazine methanone derivatives","volume":"254","author":"Zhao","year":"2023","journal-title":"J. Lumin."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"275","DOI":"10.1524\/zpch.1954.1.5_6.275","article-title":"Ein Konzentrationsumschlag der Fluoreszenz","volume":"1","author":"Kasper","year":"1954","journal-title":"Z. Phys. Chem."},{"key":"ref_6","unstructured":"Birks, J.B. (1970). Photophysics of Aromatic Molecules, Wiley."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"2559","DOI":"10.1021\/acs.accounts.9b00305","article-title":"Aggregation-induced emission luminogens for activity-based sensing","volume":"52","author":"Wang","year":"2019","journal-title":"Acc. Chem. Res."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"9888","DOI":"10.1002\/anie.201916729","article-title":"Aggregation-induced emission: New vistas at the aggregate level","volume":"59","author":"Zhao","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"9868","DOI":"10.1002\/anie.202000845","article-title":"Aggregation-induced emission: Recent advances in materials and biomedical applications","volume":"59","author":"Cai","year":"2020","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"9565","DOI":"10.1021\/acs.chemrev.6b00144","article-title":"Hexaarylbenzene: Evolution of properties and applications of multitalented scaffold","volume":"116","author":"Vij","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"3765","DOI":"10.1002\/chem.201103131","article-title":"Hetero-oligophenylene-based AIEE material as a multiple probe for biomolecules and metal ions to construct logic circuits: Application in bioelectronics and chemionics","volume":"18","author":"Bhalla","year":"2012","journal-title":"Chem. Eur. J."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"110086","DOI":"10.1016\/j.jfluchem.2023.110086","article-title":"Effects of peripheral ring fluorination on the photophysical properties of hexaarylbenzenes","volume":"266","author":"Wang","year":"2023","journal-title":"J. Fluor. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1634","DOI":"10.1039\/b101163o","article-title":"Star-like substituted hexaarylbenzenes: Synthesis and mesomorphic properties","volume":"11","author":"Geng","year":"2001","journal-title":"J. Mater. Chem."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"16190","DOI":"10.1021\/ja0765417","article-title":"Star-shaped oligo(p-phenylenevinylene) substituted hexaarylbenzene: Purity, stability, and chiral self-assembly","volume":"129","author":"George","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1699","DOI":"10.1080\/02678292.2023.2203123","article-title":"Difluoromethoxy bridged substituted 2-cyano-pyrrole based pure organic luminescent liquid crystals towards white light emitting single-molecule","volume":"50","author":"Luo","year":"2023","journal-title":"Liq. Cryst."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"553","DOI":"10.2116\/bunsekikagaku.58.553","article-title":"A simple correction method for determination of absolute fluorescence quantum yields of solid samples with a conventional fluorescence spectrophotometer","volume":"58","author":"Horigome","year":"2009","journal-title":"Bunseki Kagaku"},{"key":"ref_17","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., and Nakatsuji, H. (2016). Gaussian 16, Revision B.01, Gaussian, Inc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"1996","DOI":"10.1021\/ct800308k","article-title":"Assessment of the performance of the M05-2X and M06-2X exchange-correlation functionals for noncovalent interactions in biomolecules","volume":"4","author":"Hohenstein","year":"2008","journal-title":"J. Chem. Theory Comput."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1449","DOI":"10.1002\/jcc.20072","article-title":"Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: New energy gradients and molecular surface tesselation","volume":"25","author":"Li","year":"2004","journal-title":"J. Comput. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"8106","DOI":"10.1021\/ja9903173","article-title":"The first in situ direct observation of the light-induced radical pair from a hexaarylbiimidazolyl derivative by X-ray crystallography","volume":"121","author":"Kawano","year":"1999","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"580","DOI":"10.1002\/1521-3773(20010202)40:3<580::AID-ANIE580>3.0.CO;2-8","article-title":"EPR and density functional studies of light-induced radical pairs in a single crystal of a hexa-arylbiimidazolyl derivative","volume":"40","author":"Abe","year":"2001","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"1589","DOI":"10.1021\/ja993289x","article-title":"X-ray crystallographic study on single-crystalline photochromism of bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene","volume":"122","author":"Yamada","year":"2000","journal-title":"J. Am. Chem. Soc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"15534","DOI":"10.1002\/chem.201502473","article-title":"Photocyclodehydrofluorination","volume":"21","author":"Li","year":"2015","journal-title":"Chem. Eur. J."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"111637","DOI":"10.1016\/j.dyepig.2023.111637","article-title":"Toward high contrast photochromism materials via fluorinated TPE-based medium ring","volume":"219","author":"Zhang","year":"2023","journal-title":"Dye. Pigment."}],"container-title":["Symmetry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-8994\/16\/3\/314\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T14:10:06Z","timestamp":1760105406000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-8994\/16\/3\/314"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,3,6]]},"references-count":24,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2024,3]]}},"alternative-id":["sym16030314"],"URL":"https:\/\/doi.org\/10.3390\/sym16030314","relation":{},"ISSN":["2073-8994"],"issn-type":[{"type":"electronic","value":"2073-8994"}],"subject":[],"published":{"date-parts":[[2024,3,6]]}}}