[{"issue":"7","quality_controlled":"1","year":"2023","date_created":"2025-12-04T12:10:57Z","publisher":"American Chemical Society (ACS)","title":"Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation","publication":"Inorganic Chemistry","abstract":[{"lang":"eng","text":"Highly selective rare-earth separation has become increasingly important due to the indispensable role of these elements in various cutting-edge technologies including clean energy. However, the similar physicochemical properties of rare-earth elements (REEs) render their separation very challenging, and the development of new selective receptors for these elements is potentially of very considerable economic and environmental importance. Herein, we report the development of a series of 4-phosphoryl pyrazolone receptors for the selective separation of trivalent lanthanum, europium, and ytterbium as the representatives of light, middle, and heavy REEs, respectively. X-ray crystallography studies were employed to obtain solid-state structures across 11 of the resulting complexes, allowing comparative structure–function relationships to be probed, including the effect of lanthanide contraction that occurs along the series from lanthanum to europium to ytterbium and which potentially provides a basis for REE ion separation. In addition, the influence of ligand structure and lipophilicity on lanthanide binding and selectivity was systematically investigated via n-octanol/water distribution and liquid–liquid extraction (LLE) studies. Corresponding stoichiometry relationships between solid and solution states were well established using slope analyses. The results provide new insights into some fundamental lanthanide coordination chemistry from a separation perspective and establish 4-phosphoryl pyrazolone derivatives as potential practical extraction reagents for the selective separation of REEs in the future."}],"language":[{"iso":"eng"}],"publication_identifier":{"issn":["0020-1669","1520-510X"]},"publication_status":"published","intvolume":"        62","page":"3212-3228","citation":{"apa":"Zhang, J., Wenzel, M., Schnaars, K., Hennersdorf, F., Lindoy, L. F., &#38; Weigand, J. J. (2023). Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation. <i>Inorganic Chemistry</i>, <i>62</i>(7), 3212–3228. <a href=\"https://doi.org/10.1021/acs.inorgchem.2c04221\">https://doi.org/10.1021/acs.inorgchem.2c04221</a>","short":"J. Zhang, M. Wenzel, K. Schnaars, F. Hennersdorf, L.F. Lindoy, J.J. Weigand, Inorganic Chemistry 62 (2023) 3212–3228.","mla":"Zhang, Jianfeng, et al. “Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation.” <i>Inorganic Chemistry</i>, vol. 62, no. 7, American Chemical Society (ACS), 2023, pp. 3212–28, doi:<a href=\"https://doi.org/10.1021/acs.inorgchem.2c04221\">10.1021/acs.inorgchem.2c04221</a>.","bibtex":"@article{Zhang_Wenzel_Schnaars_Hennersdorf_Lindoy_Weigand_2023, title={Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation}, volume={62}, DOI={<a href=\"https://doi.org/10.1021/acs.inorgchem.2c04221\">10.1021/acs.inorgchem.2c04221</a>}, number={7}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Zhang, Jianfeng and Wenzel, Marco and Schnaars, Kathleen and Hennersdorf, Felix and Lindoy, Leonard F. and Weigand, Jan J.}, year={2023}, pages={3212–3228} }","ama":"Zhang J, Wenzel M, Schnaars K, Hennersdorf F, Lindoy LF, Weigand JJ. Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation. <i>Inorganic Chemistry</i>. 2023;62(7):3212-3228. doi:<a href=\"https://doi.org/10.1021/acs.inorgchem.2c04221\">10.1021/acs.inorgchem.2c04221</a>","chicago":"Zhang, Jianfeng, Marco Wenzel, Kathleen Schnaars, Felix Hennersdorf, Leonard F. Lindoy, and Jan J. Weigand. “Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation.” <i>Inorganic Chemistry</i> 62, no. 7 (2023): 3212–28. <a href=\"https://doi.org/10.1021/acs.inorgchem.2c04221\">https://doi.org/10.1021/acs.inorgchem.2c04221</a>.","ieee":"J. Zhang, M. Wenzel, K. Schnaars, F. Hennersdorf, L. F. Lindoy, and J. J. Weigand, “Highly Tunable 4-Phosphoryl Pyrazolone Receptors for Selective Rare-Earth Separation,” <i>Inorganic Chemistry</i>, vol. 62, no. 7, pp. 3212–3228, 2023, doi: <a href=\"https://doi.org/10.1021/acs.inorgchem.2c04221\">10.1021/acs.inorgchem.2c04221</a>."},"volume":62,"author":[{"first_name":"Jianfeng","last_name":"Zhang","full_name":"Zhang, Jianfeng"},{"full_name":"Wenzel, Marco","last_name":"Wenzel","first_name":"Marco"},{"first_name":"Kathleen","last_name":"Schnaars","id":"117735","full_name":"Schnaars, Kathleen"},{"last_name":"Hennersdorf","full_name":"Hennersdorf, Felix","first_name":"Felix"},{"full_name":"Lindoy, Leonard F.","last_name":"Lindoy","first_name":"Leonard F."},{"first_name":"Jan J.","last_name":"Weigand","full_name":"Weigand, Jan J."}],"date_updated":"2025-12-04T12:19:26Z","doi":"10.1021/acs.inorgchem.2c04221","type":"journal_article","status":"public","department":[{"_id":"985"}],"user_id":"117735","_id":"62854","extern":"1"},{"issue":"4","quality_controlled":"1","year":"2021","date_created":"2025-12-04T12:06:36Z","publisher":"American Chemical Society (ACS)","title":"Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex","publication":"Inorganic Chemistry","abstract":[{"lang":"eng","text":"To reduce high-level radiotoxic waste generated by nuclear power plants, highly selective separation agents for minor actinides are mandatory. The mixed N,O-donor ligand N,N,N′,N′-tetrakis[(6-carboxypyridin-2-yl)methyl]ethylenediamine (H4TPAEN; 1) has shown good performance as a masking agent in Am3+/Eu3+ separation studies. Adjustments on the pyridyl backbone to raise the hydrophilicity led to a decrease in selectivity and a decrease in M3+–Nam interactions. An enhanced basicity of the pyridyl N-donors was given as a cause. In this work, we examine whether a decrease in O-donor basicity can promote the M3+–Nam interactions. Therefore, we replace the deprotonated “charged” carboxylic acid groups of TPAEN4– by neutral amide groups and introduce N,N,N′,N’-tetrakis[(6-N″,N′′-diethylcarbamoylpyridin-2-yl)methyl]ethylenediamine (TPAMEN; 2) as a new ligand. TPAMEN was crystallized with Eu(OTf)3 and Eu(NO3)3·6H2O to form positively charged 1:1 [Eu(TPAMEN)]3+ complexes in the solid state. Alterations in the M–O/N bond distances are compared to [Eu(TPAEN)]− and investigated by DFT calculations to expose the differences in charge/energy density distributions at europium(III) and the donor functionalities of the TPAEN4– and TPAMEN. On the basis of estimations of the bond orders, atomic charges spin populations, and density of states in the Eu and potential Am and Cm complexes, the specific contributions of the donor–metal interaction are analyzed. The prediction of complex formation energy differences for the [M(TPAEN)]− and [M(TPAMEN)]3+ (M3+ = Eu3+, Am3+) complexes provide an outlook on the potential performance of TPAMEN in Am3+/Eu3+ separation."}],"language":[{"iso":"eng"}],"publication_identifier":{"issn":["0020-1669","1520-510X"]},"publication_status":"published","intvolume":"        60","page":"2477-2491","citation":{"bibtex":"@article{Schnaars_Kaneko_Fujisawa_2021, title={Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex}, volume={60}, DOI={<a href=\"https://doi.org/10.1021/acs.inorgchem.0c03405\">10.1021/acs.inorgchem.0c03405</a>}, number={4}, journal={Inorganic Chemistry}, publisher={American Chemical Society (ACS)}, author={Schnaars, Kathleen and Kaneko, Masashi and Fujisawa, Kiyoshi}, year={2021}, pages={2477–2491} }","mla":"Schnaars, Kathleen, et al. “Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex.” <i>Inorganic Chemistry</i>, vol. 60, no. 4, American Chemical Society (ACS), 2021, pp. 2477–91, doi:<a href=\"https://doi.org/10.1021/acs.inorgchem.0c03405\">10.1021/acs.inorgchem.0c03405</a>.","short":"K. Schnaars, M. Kaneko, K. Fujisawa, Inorganic Chemistry 60 (2021) 2477–2491.","apa":"Schnaars, K., Kaneko, M., &#38; Fujisawa, K. (2021). Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex. <i>Inorganic Chemistry</i>, <i>60</i>(4), 2477–2491. <a href=\"https://doi.org/10.1021/acs.inorgchem.0c03405\">https://doi.org/10.1021/acs.inorgchem.0c03405</a>","chicago":"Schnaars, Kathleen, Masashi Kaneko, and Kiyoshi Fujisawa. “Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex.” <i>Inorganic Chemistry</i> 60, no. 4 (2021): 2477–91. <a href=\"https://doi.org/10.1021/acs.inorgchem.0c03405\">https://doi.org/10.1021/acs.inorgchem.0c03405</a>.","ieee":"K. Schnaars, M. Kaneko, and K. Fujisawa, “Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex,” <i>Inorganic Chemistry</i>, vol. 60, no. 4, pp. 2477–2491, 2021, doi: <a href=\"https://doi.org/10.1021/acs.inorgchem.0c03405\">10.1021/acs.inorgchem.0c03405</a>.","ama":"Schnaars K, Kaneko M, Fujisawa K. Effect of Oxygen-Donor Charge on Adjacent Nitrogen-Donor Interactions in Eu<sup>3+</sup> Complexes of Mixed N,O-Donor Ligands Demonstrated on a 10-Fold [Eu(TPAMEN)]<sup>3+</sup> Chelate Complex. <i>Inorganic Chemistry</i>. 2021;60(4):2477-2491. doi:<a href=\"https://doi.org/10.1021/acs.inorgchem.0c03405\">10.1021/acs.inorgchem.0c03405</a>"},"volume":60,"author":[{"last_name":"Schnaars","full_name":"Schnaars, Kathleen","id":"117735","first_name":"Kathleen"},{"first_name":"Masashi","last_name":"Kaneko","full_name":"Kaneko, Masashi"},{"last_name":"Fujisawa","full_name":"Fujisawa, Kiyoshi","first_name":"Kiyoshi"}],"date_updated":"2025-12-04T12:19:31Z","doi":"10.1021/acs.inorgchem.0c03405","type":"journal_article","status":"public","department":[{"_id":"985"}],"user_id":"117735","_id":"62851","extern":"1"},{"doi":"10.1071/ch16716","date_updated":"2025-12-04T12:19:28Z","volume":70,"author":[{"full_name":"Kelly, Norman","last_name":"Kelly","first_name":"Norman"},{"first_name":"Kathleen","full_name":"Schnaars, Kathleen","id":"117735","last_name":"Schnaars"},{"first_name":"Kerstin","last_name":"Gloe","full_name":"Gloe, Kerstin"},{"last_name":"Doert","full_name":"Doert, Thomas","first_name":"Thomas"},{"last_name":"Weigand","full_name":"Weigand, Jan J.","first_name":"Jan J."},{"full_name":"Gloe, Karsten","last_name":"Gloe","first_name":"Karsten"}],"intvolume":"        70","page":"601-607","citation":{"ama":"Kelly N, Schnaars K, Gloe K, Doert T, Weigand JJ, Gloe K. New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N’-Bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamines: Synthesis and Structure*. <i>Australian Journal of Chemistry</i>. 2017;70(5):601-607. doi:<a href=\"https://doi.org/10.1071/ch16716\">10.1071/ch16716</a>","ieee":"N. Kelly, K. Schnaars, K. Gloe, T. Doert, J. J. Weigand, and K. Gloe, “New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N’-Bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamines: Synthesis and Structure*,” <i>Australian Journal of Chemistry</i>, vol. 70, no. 5, pp. 601–607, 2017, doi: <a href=\"https://doi.org/10.1071/ch16716\">10.1071/ch16716</a>.","chicago":"Kelly, Norman, Kathleen Schnaars, Kerstin Gloe, Thomas Doert, Jan J. Weigand, and Karsten Gloe. “New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N’-Bis(3-Alkoxy-2-Hydroxybenzyl)Cyclohexane-1,2-Diamines: Synthesis and Structure*.” <i>Australian Journal of Chemistry</i> 70, no. 5 (2017): 601–7. <a href=\"https://doi.org/10.1071/ch16716\">https://doi.org/10.1071/ch16716</a>.","mla":"Kelly, Norman, et al. “New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N’-Bis(3-Alkoxy-2-Hydroxybenzyl)Cyclohexane-1,2-Diamines: Synthesis and Structure*.” <i>Australian Journal of Chemistry</i>, vol. 70, no. 5, CSIRO Publishing, 2017, pp. 601–07, doi:<a href=\"https://doi.org/10.1071/ch16716\">10.1071/ch16716</a>.","bibtex":"@article{Kelly_Schnaars_Gloe_Doert_Weigand_Gloe_2017, title={New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N’-Bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamines: Synthesis and Structure*}, volume={70}, DOI={<a href=\"https://doi.org/10.1071/ch16716\">10.1071/ch16716</a>}, number={5}, journal={Australian Journal of Chemistry}, publisher={CSIRO Publishing}, author={Kelly, Norman and Schnaars, Kathleen and Gloe, Kerstin and Doert, Thomas and Weigand, Jan J. and Gloe, Karsten}, year={2017}, pages={601–607} }","short":"N. Kelly, K. Schnaars, K. Gloe, T. Doert, J.J. Weigand, K. Gloe, Australian Journal of Chemistry 70 (2017) 601–607.","apa":"Kelly, N., Schnaars, K., Gloe, K., Doert, T., Weigand, J. J., &#38; Gloe, K. (2017). New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N’-Bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamines: Synthesis and Structure*. <i>Australian Journal of Chemistry</i>, <i>70</i>(5), 601–607. <a href=\"https://doi.org/10.1071/ch16716\">https://doi.org/10.1071/ch16716</a>"},"publication_identifier":{"issn":["0004-9425","1445-0038"]},"publication_status":"published","extern":"1","_id":"62855","department":[{"_id":"985"}],"user_id":"117735","status":"public","type":"journal_article","title":"New Heterodinuclear Zn/Ln (Ln = Gd, Tb, Er, Yb) Complexes of Hexadentate N,N'-Bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamines: Synthesis and Structure*","publisher":"CSIRO Publishing","date_created":"2025-12-04T12:12:54Z","year":"2017","quality_controlled":"1","issue":"5","language":[{"iso":"eng"}],"abstract":[{"text":"<jats:p>Two N,N'-bis(3-alkoxy-2-hydroxybenzyl)cyclohexane-1,2-diamine proligands, H2L1 (R = OCH3) and H2L2 (R = OC2H5), and five heterodinuclear ZnII/LnIII complexes, [Zn(L)(µ-CH3COO)Ln(NO3)2], containing [L1]2– and Gd3+, Tb3+, Er3+, or Yb3+ and [L2]2– and Yb3+ have been synthesised and structurally characterised. The complexes are isostructural and crystallise in the P21/n monoclinic space group. Zinc(ii) is coordinated by the inner N2O2 donor set of the ligand and an oxygen of the bridging acetate anion; the lanthanide(iii) ions possess an O9 coordination environment involving the interaction with the ligand’s outer O4 donor set, two bidentate nitrate ions, and the bridging acetate.</jats:p>","lang":"eng"}],"publication":"Australian Journal of Chemistry"},{"quality_controlled":"1","publication_identifier":{"isbn":["9783319486161","9783319481357"]},"publication_status":"published","place":"Cham","year":"2016","citation":{"apa":"Wenzel, M., Schnaars, K., Kelly, N., Götzke, L., Robles, S. M., Kretschmer, K., Le, P. N., Tung, D. T., Luong, N. H., Duc, N. A., Sy, D. V., Gloe, K., &#38; Weigand, J. J. (2016). Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts. In <i>Rare Metal Technology 2016</i>. Springer International Publishing. <a href=\"https://doi.org/10.1007/978-3-319-48135-7_4\">https://doi.org/10.1007/978-3-319-48135-7_4</a>","bibtex":"@inbook{Wenzel_Schnaars_Kelly_Götzke_Robles_Kretschmer_Le_Tung_Luong_Duc_et al._2016, place={Cham}, title={Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts}, DOI={<a href=\"https://doi.org/10.1007/978-3-319-48135-7_4\">10.1007/978-3-319-48135-7_4</a>}, booktitle={Rare Metal Technology 2016}, publisher={Springer International Publishing}, author={Wenzel, M. and Schnaars, Kathleen and Kelly, N. and Götzke, L. and Robles, S. M. and Kretschmer, K. and Le, Phuc Nguyen and Tung, Dang Thanh and Luong, Nguyen Huu and Duc, Nguyen Anh and et al.}, year={2016} }","short":"M. Wenzel, K. Schnaars, N. Kelly, L. Götzke, S.M. Robles, K. Kretschmer, P.N. Le, D.T. Tung, N.H. Luong, N.A. Duc, D.V. Sy, K. Gloe, J.J. Weigand, in: Rare Metal Technology 2016, Springer International Publishing, Cham, 2016.","mla":"Wenzel, M., et al. “Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts.” <i>Rare Metal Technology 2016</i>, Springer International Publishing, 2016, doi:<a href=\"https://doi.org/10.1007/978-3-319-48135-7_4\">10.1007/978-3-319-48135-7_4</a>.","ieee":"M. Wenzel <i>et al.</i>, “Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts,” in <i>Rare Metal Technology 2016</i>, Cham: Springer International Publishing, 2016.","chicago":"Wenzel, M., Kathleen Schnaars, N. Kelly, L. Götzke, S. M. Robles, K. Kretschmer, Phuc Nguyen Le, et al. “Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts.” In <i>Rare Metal Technology 2016</i>. Cham: Springer International Publishing, 2016. <a href=\"https://doi.org/10.1007/978-3-319-48135-7_4\">https://doi.org/10.1007/978-3-319-48135-7_4</a>.","ama":"Wenzel M, Schnaars K, Kelly N, et al. Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts. In: <i>Rare Metal Technology 2016</i>. Springer International Publishing; 2016. doi:<a href=\"https://doi.org/10.1007/978-3-319-48135-7_4\">10.1007/978-3-319-48135-7_4</a>"},"date_updated":"2025-12-04T12:19:23Z","publisher":"Springer International Publishing","author":[{"full_name":"Wenzel, M.","last_name":"Wenzel","first_name":"M."},{"first_name":"Kathleen","last_name":"Schnaars","id":"117735","full_name":"Schnaars, Kathleen"},{"full_name":"Kelly, N.","last_name":"Kelly","first_name":"N."},{"first_name":"L.","full_name":"Götzke, L.","last_name":"Götzke"},{"last_name":"Robles","full_name":"Robles, S. M.","first_name":"S. M."},{"full_name":"Kretschmer, K.","last_name":"Kretschmer","first_name":"K."},{"first_name":"Phuc Nguyen","last_name":"Le","full_name":"Le, Phuc Nguyen"},{"full_name":"Tung, Dang Thanh","last_name":"Tung","first_name":"Dang Thanh"},{"first_name":"Nguyen Huu","last_name":"Luong","full_name":"Luong, Nguyen Huu"},{"last_name":"Duc","full_name":"Duc, Nguyen Anh","first_name":"Nguyen Anh"},{"last_name":"Sy","full_name":"Sy, Dang Van","first_name":"Dang Van"},{"last_name":"Gloe","full_name":"Gloe, K.","first_name":"K."},{"full_name":"Weigand, J. J.","last_name":"Weigand","first_name":"J. J."}],"date_created":"2025-12-04T12:15:35Z","title":"Hydrometallurgical Recovery of Rare Earth Metals from Spent FCC Catalysts","doi":"10.1007/978-3-319-48135-7_4","publication":"Rare Metal Technology 2016","type":"book_chapter","abstract":[{"text":"The recovery of rare earth metals from secondary sources has attracted much attention due to their ever expanding demand in the high-tech industry. The studies reported here focus on the hydrometallurgical recovery of lanthanum and cerium from spent fluid catalytic cracking (FCC) catalysts in a two-step process: leaching with nitric acid and solvent extraction by tri-n-butyl phosphate (TBP) and di(2-ethylhexyl)phosphoric acid (D2EHPA). The experiments show a high dissolution yield of about 93% lanthanum and 42% cerium in a single leaching step with 2 M (126 g/L) HNO3 at 80 °C; only 11% aluminum has been dissolved simultaneously. In the subsequent solvent extraction step the best results for this leach liquor could be achieved using a 1:1 mixture of 25% (v/v) TBP (0.92 M) and 25% (v/v) D2EHPA (0.76 M) in n-decane without the need for any pH adjustment. In that case La(III) and Ce(III) can be extracted with 60% and 74% yield respectively in one stage from the majority of accompanying matrix elements. In particular no extraction of Al(III) could be observed under these conditions.","lang":"eng"}],"status":"public","_id":"62857","department":[{"_id":"985"}],"user_id":"117735","language":[{"iso":"eng"}],"extern":"1"}]