biostudies-literatureHorii YNational University of SingaporeCore Research for Evolutional Science and TechnologyTohoku University Molecule & Material Synthesis Platform in Nanotechnology Platform ProjectBaden-WürttembergGerman-Japanese University ConsortiumCentro de Investigación Biomédica en Red en Bioingeniería, Biomateriales y Nanomedicinastate of Baden-Württemberg through bwHPC and the German Research Foundation (DFG) through grant No. INST 40/467-1 FUGG.European CommissionHigher Education Discipline Innovation ProjectGeneralitat de CatalunyaDeutsche ForschungsgemeinschaftEuropean Research CouncilBeilstein-Institut zur Förderung der Chemischen WissenschaftenMinisterio de Economía y CompetitividadJapan Society for the Promotion of Science8621-8630https://www.ebi.ac.uk/biostudies/studies/S-EPMC7384013biostudies-literatureUnknown26(39)Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of TbIII and CdII ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic 1 H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e chargeChemistry (Weinheim an der Bergstrasse, Germany)Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy.PMC7384013SEV-2015-0496FANCY CTQ2016-80030-R3068262017SGR918B18030JP14J02656ERC StG 2012-306826JP20225003JPMJCR12L3INST 40/467-1 FUGG18K14242JP15K05467R-143-000-A65-133JP24750119R-143-000-A80-11419K05401MAT2016-80826-RJP17K19102bwHPCKitagawa YHorii YBreedlove BKMas-Torrent MChibotaru LWernsdorfer WAjayakumar MRKatoh KDamjanovic MVeciana JUngur LEnders MYamashita MfalseHighly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations, Biradical Properties and Decreases in Magnetic Anisotropy.Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of TbIII and CdII ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic 1 H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e charge2020-01-01T00:00:00Z2020 Jul2025-04-19T23:01:23.947Z2025-04-19T23:01:23.947ZS-EPMC73840133242835810.1002/chem.202001365