{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,3,25]],"date-time":"2026-03-25T11:35:42Z","timestamp":1774438542087,"version":"3.50.1"},"reference-count":44,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2023,2,13]],"date-time":"2023-02-13T00:00:00Z","timestamp":1676246400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["projects UIDB\/00100\/2020, UIDP\/00100\/2020, and LA\/P\/0056\/2020 of Centro de Qu\u00edmica Estrutural, contracts IST-ID\/086\/2018 and IST-ID\/117\/2018"],"award-info":[{"award-number":["projects UIDB\/00100\/2020, UIDP\/00100\/2020, and LA\/P\/0056\/2020 of Centro de Qu\u00edmica Estrutural, contracts IST-ID\/086\/2018 and IST-ID\/117\/2018"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","doi-asserted-by":"publisher","award":["project 22BP037-13, grant for the perspective development of the scientific direction \u2018Mathematical sciences and natural sciences\u2019 at the Taras Shevchenko National University of Kyiv"],"award-info":[{"award-number":["project 22BP037-13, grant for the perspective development of the scientific direction \u2018Mathematical sciences and natural sciences\u2019 at the Taras Shevchenko National University of Kyiv"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100007684","name":"Ministry of Education and Science of Ukraine","doi-asserted-by":"publisher","award":["projects UIDB\/00100\/2020, UIDP\/00100\/2020, and LA\/P\/0056\/2020 of Centro de Qu\u00edmica Estrutural, contracts IST-ID\/086\/2018 and IST-ID\/117\/2018"],"award-info":[{"award-number":["projects UIDB\/00100\/2020, UIDP\/00100\/2020, and LA\/P\/0056\/2020 of Centro de Qu\u00edmica Estrutural, contracts IST-ID\/086\/2018 and IST-ID\/117\/2018"]}],"id":[{"id":"10.13039\/501100007684","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100007684","name":"Ministry of Education and Science of Ukraine","doi-asserted-by":"publisher","award":["project 22BP037-13, grant for the perspective development of the scientific direction \u2018Mathematical sciences and natural sciences\u2019 at the Taras Shevchenko National University of Kyiv"],"award-info":[{"award-number":["project 22BP037-13, grant for the perspective development of the scientific direction \u2018Mathematical sciences and natural sciences\u2019 at the Taras Shevchenko National University of Kyiv"]}],"id":[{"id":"10.13039\/501100007684","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Crystals"],"abstract":"<jats:p>The organic\u2013inorganic lead halide hybrids comprising semiconducting perovskite components and organic modules have proven to be promising candidates for optoelectronic applications. The modulation of the inorganic components as optical centres by diverse organic cationic templates is under intense investigation. Herein, we successfully prepared new one-dimensional lead halide hybrid perovskites [L1]2n[Pb2Cl6]n\u221e\u00b7nH2O (1) and [PbBr2(L2)]n\u221e\u00b70.5nH2O (2), and the dimeric complex [PbBr2(L3)]2 (3) in water media. In 1, 2-(2-hydroxyethyl)-2H-imidazo[1,5-a]pyridinium cation [L1]+ resulted from the oxidative condensation\u2013cyclization between formaldehyde, ethanolamine and 2-pyridinecarbaldehyde (2-PCA); the polydentate Schiff base ligands L2 and L3 formed in the in situ condensation of 2-PCA and ethanolamine or ethylenediamine, respectively. The lead chloride hybrid 1 contains the previously unreported type of a [Pb2Cl6]\u221e double chain constructed from three-edge- and five-edge-sharing PbCl6 octahedra, and cations forming \u03c0-bonded stacks aligned along the inorganic wires. In the crystal of 2, pairs of the double-side organically decorated [PbBr2(L2)]\u221e chains built of corner-sharing PbBr3N2O octahedra arrange hydrophilic channels to host water molecules. In the solid state, the identically stacked dimers of 3 form columns parallel to the ab plane with the Pb2Br4 moieties in the column being strictly coplanar. Hirshfeld surface analysis was used to rationalize the packing patterns through hydrogen bonds of O\u2212H\u00b7\u00b7\u00b7O\/Cl and C\u2212H\u00b7\u00b7\u00b7O\/Cl types with the involvement of OH groups of [L1]+, L2 and water molecules in 1 and 2, as well as C\u2013H\u2219\u2219\u2219Br hydrogen bonding in 2 and 3. The QTAIM analysis of non-covalent interactions in 1\u20133 was performed. According to the analysis of the solid-state UV\u2013visible reflectance spectra by a Tauc plot, the optical band gap values of 1, 2 and 3 as direct gap semiconductors were estimated to be 3.36, 3.13 and 2.96 eV, respectively.<\/jats:p>","DOI":"10.3390\/cryst13020307","type":"journal-article","created":{"date-parts":[[2023,2,13]],"date-time":"2023-02-13T03:07:57Z","timestamp":1676257677000},"page":"307","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["New Low-Dimensional Organic\u2013Inorganic Lead Halide Hybrid Systems Directed by Imidazo[1,5-a]pyridinium-Based Cation or Imines: Synthesis, Structures, Non-Covalent Interactions and Optical Properties"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-4315-8399","authenticated-orcid":false,"given":"Olga Yu.","family":"Vassilyeva","sequence":"first","affiliation":[{"name":"Department of Chemistry, Taras Shevchenko National University of Kyiv, 64\/13 Volodymyrska Str., 01601 Kyiv, Ukraine"}]},{"given":"Elena A.","family":"Buvaylo","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Taras Shevchenko National University of Kyiv, 64\/13 Volodymyrska Str., 01601 Kyiv, Ukraine"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0114-6525","authenticated-orcid":false,"given":"Oksana V.","family":"Nesterova","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]},{"given":"Alexandre N.","family":"Sobolev","sequence":"additional","affiliation":[{"name":"School of Molecular Sciences, M310, University of Western Australia, Perth, WA 6009, Australia"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1095-6888","authenticated-orcid":false,"given":"Dmytro S.","family":"Nesterov","sequence":"additional","affiliation":[{"name":"Centro de Qu\u00edmica Estrutural, Institute of Molecular Sciences, Instituto Superior T\u00e9cnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2023,2,13]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"668","DOI":"10.1002\/pip.2909","article-title":"Solar cell efficiency tables (version 50)","volume":"25","author":"Green","year":"2017","journal-title":"Prog. Photovolt. Res. Appl."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"295","DOI":"10.1038\/nphoton.2016.62","article-title":"Perovskite photonic sources","volume":"10","author":"Sutherland","year":"2016","journal-title":"Nat. Photon."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"4558","DOI":"10.1021\/acs.chemrev.5b00715","article-title":"Organic-Inorganic Perovskites: Structural Versatility for Functional Materials Design","volume":"116","author":"Saparov","year":"2016","journal-title":"Chem. Rev."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"4497","DOI":"10.1039\/C7SC01590A","article-title":"Structural origins of broadband emission from layered Pb\u2013Br hybrid perovskites","volume":"8","author":"Smith","year":"2017","journal-title":"Chem. Sci."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"14051","DOI":"10.1038\/ncomms14051","article-title":"One-dimensional organic lead halide perovskites with efficient bluish white-light emission","volume":"8","author":"Yuan","year":"2017","journal-title":"Nat. Commun."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"6033","DOI":"10.1039\/C8TC01150H","article-title":"White-light emission in a chiral one-dimensional organic\u2013inorganic hybrid perovskite","volume":"6","author":"Peng","year":"2018","journal-title":"J. Mater. Chem. C"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"13735","DOI":"10.1039\/C5DT01491C","article-title":"Hybrid organic\u2013inorganic chlorozincate and a molecular zinc complex involving the in situ formed imidazo [1,5-a]pyridinium cation: Serendipitous oxidative cyclization, structures and photophysical properties","volume":"44","author":"Buvaylo","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5096","DOI":"10.1039\/D0CE00018C","article-title":"Synthetic strategy towards halometallates with imidazo [1,5-a]pyridinium-based counterions","volume":"22","author":"Vassilyeva","year":"2020","journal-title":"CrystEngComm"},{"key":"ref_9","first-page":"1209","article-title":"Crystal structures of an imidazo[1,5-a] pyridinium-based ligand and its (C13H12N3)2[CdI4] hybrid salt","volume":"75","author":"Vassilyeva","year":"2019","journal-title":"Acta Cryst."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"11278","DOI":"10.1039\/C9DT01642B","article-title":"Long magnetic relaxation time of tetracoordinate Co2+ in imidazo [1,5-a]pyridinium-based (C13H12N3)2[CoCl4] hybrid salt and [Co(C13H12N3)Cl3] molecular complex","volume":"48","author":"Vassilyeva","year":"2019","journal-title":"Dalton Trans."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"7713","DOI":"10.1039\/D0RA10787E","article-title":"Organic\u2013inorganic hybrid tetrachlorocadmates as promising fluorescent agents for cross-linked polyurethanes: Synthesis, crystal structures and extended performance analysis","volume":"11","author":"Vassilyeva","year":"2021","journal-title":"RSC Adv."},{"key":"ref_12","first-page":"359","article-title":"Organic-inorganic hybrid mixed-halide ZnII and CdII tetrahalometallates with the 2-methylimidazo[1,5-a]pyridinium cation","volume":"78","author":"Vassilyeva","year":"2022","journal-title":"Acta Cryst."},{"key":"ref_13","doi-asserted-by":"crossref","unstructured":"Lyons, A.S., Ingersoll, M.A., Muniyan, S., D\u2019Cunha, N., Robinson, T., Hoelting, K., Dwyer, J.G., Biu, X.R., Batra, S.K., and Lin, M.F. (2015). Novel imidazopyridine derivatives possess anti-tumor effect on human castration-resistant prostate cancer cells. PLoS ONE, 10.","DOI":"10.1371\/journal.pone.0131811"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"41317","DOI":"10.1039\/C5RA25947A","article-title":"A ratiometric lysosomal pH probe based on the imidazo[1,5-a]pyridine\u2013rhodamine FRET and ICT system","volume":"6","author":"Song","year":"2016","journal-title":"RSC Adv."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"109455","DOI":"10.1016\/j.dyepig.2021.109455","article-title":"Strategies to increase the quantum yield: Luminescent methoxylated imidazo[1,5-a]pyridines","volume":"192","author":"Volpi","year":"2021","journal-title":"Dyes Pigment."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1614","DOI":"10.1002\/ajoc.201800250","article-title":"Fluorescent N-heteroarenes having large stokes shift and water solubility suitable for bioimaging","volume":"7","author":"Yagishita","year":"2018","journal-title":"Asian J. Org. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"333","DOI":"10.1002\/anie.196303331","article-title":"Principles and techniques of diffuse-reflectance spectroscopy","volume":"2","author":"Braun","year":"1963","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"114573","DOI":"10.1016\/j.ssc.2021.114573","article-title":"Use and misuse of the Kubelka-Munk function to obtain the band gap energy from diffuse reflectance measurements","volume":"341","author":"Landi","year":"2022","journal-title":"Solid State Commun."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1006","DOI":"10.1107\/S1600576721002910","article-title":"CrystalExplorer: A program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals","volume":"54","author":"Spackman","year":"2021","journal-title":"J. Appl. Cryst."},{"key":"ref_20","first-page":"3","article-title":"Crystal structure refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Cryst."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"e1606","DOI":"10.1002\/wcms.1606","article-title":"Software update: The ORCA program system\u2014Version 5.0","volume":"12","author":"Neese","year":"2022","journal-title":"Wil. Interdiscip. Rev. Comput. Mol. Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"73","DOI":"10.1002\/wcms.81","article-title":"The ORCA program system","volume":"2","author":"Neese","year":"2012","journal-title":"Wil. Interdiscip. Rev. Comput. Mol. Sci."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"214110","DOI":"10.1063\/1.4952647","article-title":"\u03c9B97M-V: A combinatorially optimized, range-separated hybrid, meta-GGA density functional with VV10 nonlocal correlation","volume":"144","author":"Mardirossian","year":"2016","journal-title":"J. Chem. Phys."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3297","DOI":"10.1039\/b508541a","article-title":"Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy","volume":"7","author":"Weigend","year":"2005","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1292","DOI":"10.1007\/s00214-012-1292-x","article-title":"All-electron scalar relativistic basis sets for the 6p elements","volume":"131","author":"Pantazis","year":"2012","journal-title":"Theor. Chem. Acc."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"1057","DOI":"10.1039\/b515623h","article-title":"Accurate Coulomb-fitting basis sets for H to Rn","volume":"8","author":"Weigend","year":"2006","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"554","DOI":"10.1021\/acs.jctc.6b01041","article-title":"Automatic Generation of Auxiliary Basis Sets","volume":"13","author":"Stoychev","year":"2017","journal-title":"J. Chem. Theor. Comput."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"392","DOI":"10.1063\/1.476576","article-title":"Molecular density functional calculations in the regular relativistic approximation: Method, application to coinage metal diatomics, hydrides, fluorides and chlorides, and comparison with first-order relativistic calculations","volume":"109","year":"1998","journal-title":"J. Chem. Phys."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1995","DOI":"10.1021\/jp9716997","article-title":"Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model","volume":"102","author":"Barone","year":"1998","journal-title":"J. Phys. Chem. A"},{"key":"ref_30","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_31","doi-asserted-by":"crossref","first-page":"6498","DOI":"10.1021\/ja100936w","article-title":"Revealing Noncovalent Interactions","volume":"132","author":"Johnson","year":"2010","journal-title":"J. Am. Chem. Soc."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"33","DOI":"10.1016\/0263-7855(96)00018-5","article-title":"VMD\u2014Visual Molecular Dynamics","volume":"14","author":"Humphrey","year":"1996","journal-title":"J. Mol. Graph."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"577","DOI":"10.1039\/b713261a","article-title":"Inorganic\u2013organic hybrid salts of diaminobenzenes and related cations","volume":"10","author":"Dobrzycki","year":"2008","journal-title":"CrystEngComm"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"24253","DOI":"10.1021\/acs.jpcc.8b06850","article-title":"Yellowish white-light emission involving resonant energy transfer in a new one-dimensional hybrid material: (C9H10N2)PbCl4","volume":"122","author":"Barkaoui","year":"2018","journal-title":"J. Phys. Chem. C"},{"key":"ref_35","first-page":"171","article-title":"The Cambridge Structural Database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Cryst."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1443","DOI":"10.1021\/acsenergylett.8b00661","article-title":"A one-dimensional organic lead chloride hybrid with excitation-dependent broadband emissions","volume":"3","author":"Wu","year":"2018","journal-title":"ACS Energy Lett."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2191","DOI":"10.1039\/c2sc20045g","article-title":"Rethinking the term \u201cpi-stacking\u201d","volume":"3","author":"Martinez","year":"2012","journal-title":"Chem. Sci."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"1491","DOI":"10.1021\/acs.inorgchem.0c02785","article-title":"Combining dual-light emissions to achieve efficient broadband yellowish-green luminescence in one-dimensional hybrid lead halides","volume":"60","author":"Sun","year":"2021","journal-title":"Inorg. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"13078","DOI":"10.1021\/jacs.8b08691","article-title":"Structural diversity in white-light-emitting hybrid lead bromide perovskites","volume":"140","author":"Mao","year":"2018","journal-title":"JACS"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"328","DOI":"10.1016\/j.molstruc.2013.08.016","article-title":"Syntheses, structures, and luminescence behavior of terephthalate bridged lead(II) complexes with tetradentate N-donor Schiff bases","volume":"1051","author":"Roy","year":"2013","journal-title":"J. Mol. Struct."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"4088","DOI":"10.1080\/00958972.2011.634908","article-title":"Sonochemical synthesis of nano-structured lead(II) complex: Precursor for the preparation of PbO nano-structures","volume":"64","author":"Hashemi","year":"2011","journal-title":"J. Coord. Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"2868","DOI":"10.1002\/jcc.26068","article-title":"Exploring Nature and Predicting Strength of Hydrogen Bonds: A Correlation Analysis between Atoms-in-Molecules Descriptors, Binding Energies, and Energy Components of Symmetry-Adapted Perturbation Theory","volume":"40","author":"Emamian","year":"2019","journal-title":"J. Comput. Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"12983","DOI":"10.1021\/jp204278k","article-title":"Analysis of Hydrogen-Bond Interaction Potentials from the Electron Density: Integration of Noncovalent Interaction Regions","volume":"115","author":"Yang","year":"2011","journal-title":"J. Phys. Chem. A"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"8408","DOI":"10.1021\/acs.inorgchem.7b01096","article-title":"The role of connectivity on electronic properties of lead iodide perovskite-derived compounds","volume":"56","author":"Kamminga","year":"2017","journal-title":"Inorg. Chem."}],"container-title":["Crystals"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4352\/13\/2\/307\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T18:33:08Z","timestamp":1760121188000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4352\/13\/2\/307"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,2,13]]},"references-count":44,"journal-issue":{"issue":"2","published-online":{"date-parts":[[2023,2]]}},"alternative-id":["cryst13020307"],"URL":"https:\/\/doi.org\/10.3390\/cryst13020307","relation":{},"ISSN":["2073-4352"],"issn-type":[{"value":"2073-4352","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,2,13]]}}}