Qingqing Yang, Ning Guo, Tieyan Chang, Zheng Guo, Xiaoli Wang, Chuanyan Fan, Chao Liu, Lu Han, Feiyu Li, Tao He, Qiang Zheng, Yu-Sheng Chen, Junjie Zhang
{"title":"La3Pd2NaO9：一种高价绝缘钯酸盐。","authors":"Qingqing Yang, Ning Guo, Tieyan Chang, Zheng Guo, Xiaoli Wang, Chuanyan Fan, Chao Liu, Lu Han, Feiyu Li, Tao He, Qiang Zheng, Yu-Sheng Chen, Junjie Zhang","doi":"10.1021/acs.inorgchem.5c01833","DOIUrl":null,"url":null,"abstract":"<p><p>A high-valent palladate, La<sub>3</sub>Pd<sub>2</sub>NaO<sub>9</sub>, has been synthesized for the first time. Single crystals with dimensions of 20 μm on the edge were successfully grown using the flux method at 420 °C and 70 bar oxygen pressure. Energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectroscopy (ICP) measurements show that the atomic ratio of La: (Pd + Na) is 3:3 and Pd: Na is 2:1. X-ray photoelectron spectroscopy (XPS) measurements show that the oxidation state of Pd is dominated by the +4. Synchrotron X-ray single-crystal diffraction measurements revealed that this material crystallizes in the monoclinic <i>P</i>2<sub>1</sub>/<i>c</i> space group with charge ordering of Na and Pd. Real-space imaging via scanning transmission electron microscopy (STEM) confirmed the crystal structure and revealed excellent sample homogeneity. Electrical resistivity measurements show an insulating behavior. Magnetic measurements show an unexpected paramagnetic behavior, which probably originates from a small fraction of high-spin Pd<sup>2+</sup> evidenced by XPS. The successful growth of La<sub>3</sub>Pd<sub>2</sub>NaO<sub>9</sub> single crystals with a high-valent oxidation state of Pd offers an approach for exploring interesting palladates, including potential bilayer Ruddlesden-Popper palladates analogous to the high temperature superconducting La<sub>3</sub>Ni<sub>2</sub>O<sub>7</sub>.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"13887-13896"},"PeriodicalIF":4.7000,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"La<sub>3</sub>Pd<sub>2</sub>NaO<sub>9</sub>: A High-Valent Insulating Palladate.\",\"authors\":\"Qingqing Yang, Ning Guo, Tieyan Chang, Zheng Guo, Xiaoli Wang, Chuanyan Fan, Chao Liu, Lu Han, Feiyu Li, Tao He, Qiang Zheng, Yu-Sheng Chen, Junjie Zhang\",\"doi\":\"10.1021/acs.inorgchem.5c01833\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>A high-valent palladate, La<sub>3</sub>Pd<sub>2</sub>NaO<sub>9</sub>, has been synthesized for the first time. Single crystals with dimensions of 20 μm on the edge were successfully grown using the flux method at 420 °C and 70 bar oxygen pressure. Energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectroscopy (ICP) measurements show that the atomic ratio of La: (Pd + Na) is 3:3 and Pd: Na is 2:1. X-ray photoelectron spectroscopy (XPS) measurements show that the oxidation state of Pd is dominated by the +4. Synchrotron X-ray single-crystal diffraction measurements revealed that this material crystallizes in the monoclinic <i>P</i>2<sub>1</sub>/<i>c</i> space group with charge ordering of Na and Pd. Real-space imaging via scanning transmission electron microscopy (STEM) confirmed the crystal structure and revealed excellent sample homogeneity. Electrical resistivity measurements show an insulating behavior. Magnetic measurements show an unexpected paramagnetic behavior, which probably originates from a small fraction of high-spin Pd<sup>2+</sup> evidenced by XPS. The successful growth of La<sub>3</sub>Pd<sub>2</sub>NaO<sub>9</sub> single crystals with a high-valent oxidation state of Pd offers an approach for exploring interesting palladates, including potential bilayer Ruddlesden-Popper palladates analogous to the high temperature superconducting La<sub>3</sub>Ni<sub>2</sub>O<sub>7</sub>.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\" \",\"pages\":\"13887-13896\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-07-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.inorgchem.5c01833\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2025/6/29 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.5c01833","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/6/29 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
A high-valent palladate, La3Pd2NaO9, has been synthesized for the first time. Single crystals with dimensions of 20 μm on the edge were successfully grown using the flux method at 420 °C and 70 bar oxygen pressure. Energy dispersive spectroscopy (EDS) and inductively coupled plasma mass spectroscopy (ICP) measurements show that the atomic ratio of La: (Pd + Na) is 3:3 and Pd: Na is 2:1. X-ray photoelectron spectroscopy (XPS) measurements show that the oxidation state of Pd is dominated by the +4. Synchrotron X-ray single-crystal diffraction measurements revealed that this material crystallizes in the monoclinic P21/c space group with charge ordering of Na and Pd. Real-space imaging via scanning transmission electron microscopy (STEM) confirmed the crystal structure and revealed excellent sample homogeneity. Electrical resistivity measurements show an insulating behavior. Magnetic measurements show an unexpected paramagnetic behavior, which probably originates from a small fraction of high-spin Pd2+ evidenced by XPS. The successful growth of La3Pd2NaO9 single crystals with a high-valent oxidation state of Pd offers an approach for exploring interesting palladates, including potential bilayer Ruddlesden-Popper palladates analogous to the high temperature superconducting La3Ni2O7.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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