{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,30]],"date-time":"2026-10-30T14:47:01Z","timestamp":1793371621770,"version":"4.5.0"},"reference-count":39,"publisher":"American Chemical Society (ACS)","issue":"25","license":[{"start":{"date-parts":[[2019,6,17]],"date-time":"2019-06-17T00:00:00Z","timestamp":1560729600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccby_termsofuse.html"}],"funder":[{"DOI":"10.13039\/100000082","name":"Division of Graduate Education","doi-asserted-by":"publisher","award":["DGE-1324585"],"award-info":[{"award-number":["DGE-1324585"]}],"id":[{"id":"10.13039\/100000082","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2019,6,26]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Low-dimensional metal halides have been researched as optoelectronic materials for the past two decades. Zero-dimensional halides of ns2 elements (Sn, Pb, Sb) have recently gained attention as highly efficient broadband light emitters. These compounds comprise discrete metal halide centers, isolated by bulky organic cations. Herein, we report isostructural halide complexes of Ge(II), Sn(II), and Pb(II) with a 1-butyl-1-methyl-piperidinium cation (Bmpip), featuring unusual disphenoidal coordination with a highly stereoactive lone pair. Spectrally broad, bright emission from highly localized excitons, with quantum efficiencies of up to 75%, is observed in blue to red spectral regions for bromides (for Pb, Sn, and Ge, respectively) and extends into the near-infrared for Bmpip2SnI4 (peak at 730 nm). In the case of Sn(II) and Ge(II), both singlet and triplet excitonic emission bands have been observed. Furthermore, Bmpip2SnBr4 and Bmpip2PbBr4 exhibit X-ray-excited luminescence (radioluminescence) with brightness being commensurate with that of a commercial inorganic X-ray scintillator (NaI:Tl).<\/jats:p>","DOI":"10.1021\/jacs.9b02365","type":"journal-article","created":{"date-parts":[[2019,6,17]],"date-time":"2019-06-17T12:41:11Z","timestamp":1560775271000},"page":"9764-9768","source":"Crossref","is-referenced-by-count":560,"title":["Disphenoidal\nZero-Dimensional Lead, Tin, and Germanium\nHalides: Highly Emissive Singlet and Triplet Self-Trapped Excitons\nand X-ray Scintillation"],"prefix":"10.1021","volume":"141","author":[{"given":"Viktoriia","family":"Morad","sequence":"first","affiliation":[{"name":"ETH Zu\u0308rich , , Vladimir Prelog Weg 1 , ,","place":["Zu\u0308rich, Switzerland, CH-8093"]},{"name":"Empa\u2500Swiss Federal Laboratories for Materials Science and Technology , , U\u0308berlandstrasse 129 , ,","place":["Du\u0308bendorf, Switzerland, CH-8600"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1587-1752","authenticated-orcid":true,"given":"Yevhen","family":"Shynkarenko","sequence":"additional","affiliation":[{"name":"ETH Zu\u0308rich , , Vladimir Prelog Weg 1 , ,","place":["Zu\u0308rich, Switzerland, CH-8093"]},{"name":"Empa\u2500Swiss Federal Laboratories for Materials Science and Technology , , U\u0308berlandstrasse 129 , ,","place":["Du\u0308bendorf, Switzerland, CH-8600"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6409-0565","authenticated-orcid":true,"given":"Sergii","family":"Yakunin","sequence":"additional","affiliation":[{"name":"ETH Zu\u0308rich , , Vladimir Prelog Weg 1 , ,","place":["Zu\u0308rich, Switzerland, CH-8093"]},{"name":"Empa\u2500Swiss Federal Laboratories for Materials Science and Technology , , U\u0308berlandstrasse 129 , ,","place":["Du\u0308bendorf, Switzerland, CH-8600"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2512-4686","authenticated-orcid":true,"given":"Alexandra","family":"Brumberg","sequence":"additional","affiliation":[{"name":"Northwestern University , , 2145 Sheridan Road , , ,","place":["Evanston, Illinois, United States, 60208"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9696-8830","authenticated-orcid":true,"given":"Richard D.","family":"Schaller","sequence":"additional","affiliation":[{"name":"Northwestern University , , 2145 Sheridan Road , , ,","place":["Evanston, Illinois, United States, 60208"]},{"name":"Argonne National Laboratory , , 9700 Cass Avenue , , ,","place":["Lemont, Illinois, United States, 60439"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6396-8938","authenticated-orcid":true,"given":"Maksym V.","family":"Kovalenko","sequence":"additional","affiliation":[{"name":"ETH Zu\u0308rich , , Vladimir Prelog Weg 1 , ,","place":["Zu\u0308rich, Switzerland, CH-8093"]},{"name":"Empa\u2500Swiss Federal Laboratories for Materials Science and Technology , , U\u0308berlandstrasse 129 , ,","place":["Du\u0308bendorf, Switzerland, CH-8600"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2019,6,17]]},"reference":[{"issue":"5","key":"2026090217411493100_cit1a","doi-asserted-by":"publisher","first-page":"391","DOI":"10.1038\/nnano.2015.90","article-title":"Metal-Halide Perovskites for Photovoltaic\nand Light-Emitting Devices","volume":"10","author":"Stranks","year":"2015","journal-title":"Nat. Nanotechnol."},{"issue":"7732","key":"2026090217411493100_cit1b","doi-asserted-by":"publisher","first-page":"541","DOI":"10.1038\/s41586-018-0691-0","article-title":"Efficient and stable emission of\nwarm-white light from lead-free halide double perovskites","volume":"563","author":"Luo","year":"2018","journal-title":"Nature"},{"issue":"6431","key":"2026090217411493100_cit2","doi-asserted-by":"publisher","first-page":"1068","DOI":"10.1126\/science.aau7392","article-title":"Coherent single-photon\nemission from colloidal lead halide perovskite quantum dots","volume":"363","author":"Utzat","year":"2019","journal-title":"Science"},{"issue":"7458","key":"2026090217411493100_cit3a","doi-asserted-by":"publisher","first-page":"316","DOI":"10.1038\/nature12340","article-title":"Sequential Deposition\nas a Route to High-Performance Perovskite-Sensitized Solar Cells","volume":"499","author":"Burschka","year":"2013","journal-title":"Nature"},{"issue":"6107","key":"2026090217411493100_cit3b","doi-asserted-by":"publisher","first-page":"643","DOI":"10.1126\/science.1228604","article-title":"Efficient Hybrid Solar Cells Based on Meso-Superstructured\nOrganometal Halide Perovskites","volume":"338","author":"Lee","year":"2012","journal-title":"Science"},{"issue":"9","key":"2026090217411493100_cit3c","doi-asserted-by":"publisher","first-page":"585","DOI":"10.1038\/nphoton.2016.139","article-title":"Detection\nof Gamma Photons Using Solution-Grown Single Crystals of Hybrid Lead\nHalide Perovskites","volume":"10","author":"Yakunin","year":"2016","journal-title":"Nat. Photonics"},{"issue":"7","key":"2026090217411493100_cit3d","doi-asserted-by":"publisher","first-page":"2722","DOI":"10.1021\/cg400645t","article-title":"Crystal\nGrowth of the Perovskite Semiconductor CsPbBr3: A New Material\nfor High-Energy Radiation Detection","volume":"13","author":"Stoumpos","year":"2013","journal-title":"Cryst.\nGrowth Des."},{"key":"2026090217411493100_cit3e","doi-asserted-by":"publisher","first-page":"5404","DOI":"10.1038\/ncomms6404","article-title":"Solution-Processed Hybrid Perovskite Photodetectors\nWith High Detectivity","volume":"5","author":"Dou","year":"2014","journal-title":"Nat. Commun."},{"issue":"46","key":"2026090217411493100_cit3f","doi-asserted-by":"publisher","first-page":"7373","DOI":"10.1002\/adfm.201402020","article-title":"High-Performance Flexible Broadband\nPhotodetector Based on Organolead Halide Perovskite","volume":"24","author":"Hu","year":"2014","journal-title":"Adv. Funct. Mater."},{"key":"2026090217411493100_cit3g","doi-asserted-by":"publisher","first-page":"e431","DOI":"10.1038\/am.2017.163","article-title":"Non-Dissipative Internal Optical Filtering with Solution-Grown\nPerovskite Single Crystals for Full-Colour Imaging","volume":"9","author":"Yakunin","year":"2017","journal-title":"NPG Asia Mater."},{"issue":"3","key":"2026090217411493100_cit4a","doi-asserted-by":"publisher","first-page":"850","DOI":"10.1021\/ja4109209","article-title":"Nontemplate\nSynthesis of CH3NH3PbBr3 Perovskite\nNanoparticles","volume":"136","author":"Schmidt","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026090217411493100_cit4b","doi-asserted-by":"publisher","first-page":"3692","DOI":"10.1021\/nl5048779","article-title":"Nanocrystals\nof Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br,\nand I): Novel Optoelectronic Materials Showing Bright Emission with\nWide Color Gamut","volume":"15","author":"Protesescu","year":"2015","journal-title":"Nano Lett."},{"key":"2026090217411493100_cit4c","doi-asserted-by":"publisher","first-page":"3296","DOI":"10.1021\/acs.chemrev.8b00644","article-title":"Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications,\nand Their Optical Properties","volume":"119","author":"Shamsi","year":"2019","journal-title":"Chem. Rev."},{"issue":"40","key":"2026090217411493100_cit5a","doi-asserted-by":"publisher","first-page":"13078","DOI":"10.1021\/jacs.8b08691","article-title":"Structural Diversity in White-Light-Emitting\nHybrid Lead Bromide Perovskites","volume":"140","author":"Mao","year":"2018","journal-title":"J. Am. Chem.\nSoc."},{"issue":"1","key":"2026090217411493100_cit5b","doi-asserted-by":"publisher","first-page":"54","DOI":"10.1021\/acsenergylett.7b00926","article-title":"Low-Dimensional\nOrganometal Halide Perovskites","volume":"3","author":"Lin","year":"2018","journal-title":"ACS Energy Lett."},{"issue":"40","key":"2026090217411493100_cit6a","doi-asserted-by":"publisher","first-page":"34363","DOI":"10.1021\/acsami.8b07673","article-title":"Hollow Two-Dimensional\nTin Bromide Perovskite with Tunable Broadband\nEmission","volume":"10","author":"Fu","year":"2018","journal-title":"ACS Appl. Mater. Interfaces"},{"issue":"38","key":"2026090217411493100_cit6b","doi-asserted-by":"publisher","first-page":"13154","DOI":"10.1021\/ja507086b","article-title":"Intrinsic White-Light Emission from Layered Hybrid\nPerovskites","volume":"136","author":"Dohner","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"3","key":"2026090217411493100_cit6c","doi-asserted-by":"publisher","first-page":"619","DOI":"10.1021\/acs.accounts.7b00433","article-title":"White-Light\nEmission from Layered Halide Perovskites","volume":"51","author":"Smith","year":"2018","journal-title":"Acc.\nChem. Res."},{"issue":"5","key":"2026090217411493100_cit6d","doi-asserted-by":"publisher","first-page":"1718","DOI":"10.1021\/ja411045r","article-title":"Self-Assembly of Broadband White-Light\nEmitters","volume":"136","author":"Dohner","year":"2014","journal-title":"J. Am. Chem. Soc."},{"issue":"35","key":"2026090217411493100_cit7a","doi-asserted-by":"publisher","first-page":"11329","DOI":"10.1002\/anie.201806452","article-title":"Highly\nEmissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional\nTin Halides","volume":"57","author":"Benin","year":"2018","journal-title":"Angew. Chem., Int. Ed."},{"issue":"3","key":"2026090217411493100_cit7b","doi-asserted-by":"publisher","first-page":"586","DOI":"10.1039\/C7SC04539E","article-title":"Luminescent zero-dimensional\norganic metal halide hybrids with near-unity quantum efficiency","volume":"9","author":"Zhou","year":"2018","journal-title":"Chem. Sci."},{"issue":"6","key":"2026090217411493100_cit7c","doi-asserted-by":"publisher","first-page":"1337","DOI":"10.1021\/acs.jpclett.9b00238","article-title":"Broad-Band\nEmission in a Zero-Dimensional Hybrid Organic [PbBr6] Trimer with\nIntrinsic Vacancies","volume":"10","author":"Zhou","year":"2019","journal-title":"J. Phys. Chem. Lett."},{"issue":"3","key":"2026090217411493100_cit7d","doi-asserted-by":"publisher","first-page":"269","DOI":"10.1021\/acsaelm.9b00015","article-title":"Near-Unity\nPhotoluminescence Quantum Yield in Blue-Emitting Cs3Cu2Br5\u2013xIx\n(0 \u2264 x \u2264 5)","volume":"1","author":"Roccanova","year":"2019","journal-title":"ACS Applied Electronic Materials"},{"issue":"4","key":"2026090217411493100_cit8","doi-asserted-by":"publisher","first-page":"245","DOI":"10.1080\/02603599308048663","article-title":"The Structures of s2 Metal Complexes in the Ground and sp Excited\nStates","volume":"14","author":"Vogler","year":"1993","journal-title":"Comments Inorg.\nChem."},{"issue":"5","key":"2026090217411493100_cit9a","doi-asserted-by":"publisher","first-page":"251","DOI":"10.1016\/0375-9601(71)90855-3","article-title":"Luminescence of Lead Chloride and\nLead Bromide Single Crystals","volume":"34","author":"Degruijter","year":"1971","journal-title":"Phys. Lett. A"},{"issue":"16","key":"2026090217411493100_cit9b","doi-asserted-by":"publisher","first-page":"10766","DOI":"10.1103\/PhysRevB.62.10766","article-title":"Charge Separation of Excitons and the Radiative Recombination\nProcess in PbBr2 Crystals","volume":"62","author":"Iwanaga","year":"2000","journal-title":"Phys.\nRev. B: Condens. Matter Mater. Phys."},{"issue":"6","key":"2026090217411493100_cit9c","doi-asserted-by":"publisher","first-page":"4304","DOI":"10.1103\/PhysRevB.66.064304","article-title":"Self-Trapped\nStates and Related Luminescence in PbCl2 Crystals","volume":"66","author":"Iwanaga","year":"2002","journal-title":"Phys. Rev. B: Condens. Matter Mater. Phys."},{"issue":"8","key":"2026090217411493100_cit9d","doi-asserted-by":"publisher","first-page":"3539","DOI":"10.1063\/1.3576118","article-title":"Optical Properties of SnCl2 Phosphor","volume":"109","author":"Nara","year":"2011","journal-title":"J. Appl. Phys."},{"issue":"2","key":"2026090217411493100_cit9e","doi-asserted-by":"publisher","first-page":"217","DOI":"10.1016\/0022-2313(77)90020-5","article-title":"Photoluminescence of PbBr2, PbCl2 and Beta-PbF2 Single-Crystals","volume":"15","author":"Eijkelenkamp","year":"1977","journal-title":"J. Lumin."},{"issue":"2","key":"2026090217411493100_cit9f","doi-asserted-by":"publisher","first-page":"71","DOI":"10.1016\/0022-2313(73)90042-2","article-title":"Low-Temperature X-ray and Photoluminescence of Lead\nHalide Crystals","volume":"6","author":"Liidja","year":"1973","journal-title":"J. Lumin."},{"issue":"2","key":"2026090217411493100_cit10","doi-asserted-by":"publisher","first-page":"489","DOI":"10.1021\/acs.jpclett.6b02800","article-title":"High Defect Tolerance\nin Lead Halide Perovskite CsPbBr3","volume":"8","author":"Kang","year":"2017","journal-title":"J. Phys. Chem. Lett."},{"issue":"2","key":"2026090217411493100_cit11a","doi-asserted-by":"publisher","first-page":"251","DOI":"10.1515\/ncrs-2000-0229","article-title":"Crystal Structure of 1,2-Vinylenbis(triphenylphosphonium)\nDibromide Dihydrate, [Ph3P-CH = CH-PPh3][Br]2\u00b72H2O","volume":"215","author":"Blachnik","year":"2000","journal-title":"Z. Kristallogr.\n- New Cryst. Struct."},{"issue":"1","key":"2026090217411493100_cit11b","doi-asserted-by":"publisher","first-page":"57","DOI":"10.1002\/1521-3749(200201)628:1&lt;57::AID-ZAAC57&gt;3.0.CO;2-P","article-title":"Bromoplumbate mit Kettenfo\u0308rmigen\nund Isolierten Anionen: (Bzl4P)2[Pb3Br8], (Bzl4P)2[Pb3Br8(dmf)2], (Bzl4P)[PbBr3],\n(Bzl4P)2[PbBr4] und (Bzl4P)4[Pb2Br6][PbBr4]","volume":"628","author":"Gro\u0308ger","year":"2002","journal-title":"Z. Anorg. Allg. Chem."},{"issue":"9","key":"2026090217411493100_cit12","doi-asserted-by":"publisher","first-page":"2159","DOI":"10.1021\/acsenergylett.8b01226","article-title":"Spin-Orbit Interactions\nGreatly Accelerate Nonradiative Dynamics in Lead Halide Perovskites","volume":"3","author":"Li","year":"2018","journal-title":"ACS Energy Lett."},{"issue":"1","key":"2026090217411493100_cit13","doi-asserted-by":"publisher","first-page":"35","DOI":"10.1016\/0022-3697(91)90059-9","article-title":"Alkali-Halide\nCrystals Containing Impurity Ions with the ns2 Ground-State\nElectronic Configuration","volume":"52","author":"Jacobs","year":"1991","journal-title":"J. Phys. Chem. Solids"},{"issue":"40","key":"2026090217411493100_cit14a","doi-asserted-by":"publisher","first-page":"18868","DOI":"10.1021\/jp051822r","article-title":"Influence of the\nAnion on Lone Pair Formation in Sn(II) Monochalcogenides: A DFT Study","volume":"109","author":"Walsh","year":"2005","journal-title":"J. Phys. Chem. B"},{"issue":"5","key":"2026090217411493100_cit14b","doi-asserted-by":"publisher","first-page":"1422","DOI":"10.1016\/j.jssc.2005.01.030","article-title":"The Origin of the Stereochemically\nActive Pb(II) Lone Pair: DFT Calculations on PbO and PbS","volume":"178","author":"Walsh","year":"2005","journal-title":"J. Solid State Chem."},{"issue":"15","key":"2026090217411493100_cit15","doi-asserted-by":"publisher","first-page":"3277","DOI":"10.1021\/ic00041a021","article-title":"Photoluminescence\nof Germanium(II),\nTin(II), and Lead(II) Chloride Complexes in Solution","volume":"31","author":"Nikol","year":"1992","journal-title":"Inorg. Chem."},{"issue":"36","key":"2026090217411493100_cit16","doi-asserted-by":"publisher","first-page":"30051","DOI":"10.1021\/acsami.8b12474","article-title":"Sunlike White-Light-Emitting\nDiodes\nBased on Zero-Dimensional Organic Metal Halide Hybrids","volume":"10","author":"Worku","year":"2018","journal-title":"ACS Appl. Mater. Interfaces"}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.9b02365","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/141\/25\/9764\/15296766\/ja9b02365.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/141\/25\/9764\/15296766\/ja9b02365.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T21:41:26Z","timestamp":1788385286000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/141\/25\/9764\/1451334\/Disphenoidal-Zero-Dimensional-Lead-Tin-and"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,6,17]]},"references-count":39,"journal-issue":{"issue":"25","published-online":{"date-parts":[[2019,6,17]]},"published-print":{"date-parts":[[2019,6,26]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.9b02365","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,6,17]]}}}