A study of cation-dependent inverse hydrogen bonds and magnetic exchange-couplings in lanthanacarborane complexes
Peng-Bo Jin,
Qian-Cheng Luo,
Yuan-Qi Zhai,
Yi-Dian Wang,
Yan Ma,
Lei Tian,
Xinliang Zhang,
Chao Ke,
Xu-Feng Zhang,
Yi Lv,
Yan-Zhen Zheng
Affiliations
Peng-Bo Jin
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory for Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter and School of Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, P.R. China
Qian-Cheng Luo
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory for Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter and School of Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, P.R. China
Yuan-Qi Zhai
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory for Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter and School of Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, P.R. China
Yi-Dian Wang
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory for Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter and School of Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, P.R. China
Yan Ma
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory for Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter and School of Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, P.R. China
Lei Tian
State Key Laboratory of Military Stomatology, National Clinical Research Center of Oral Diseases, Shaanxi Key Laboratory of Oral Diseases, Department of Cranio-facial Trauma and Orthognathic Surgery, School of Stomatology, The Fourth Military Medical University, Xi'an, No. 145, Changle Xi Road, 710032 Xi'an, Shaanxi, P.R. China
Xinliang Zhang
Department of Spine Surgery, Honghui Hospital, Xi'an Jiaotong University, 710054 Xi'an, Shaanxi, P.R. China
Chao Ke
Department of Orthopaedic Trauma, Honghui Hospital, College of Medicine, Xi'an Jiaotong University, 710054 Xi'an, Shaanxi, P.R. China
Xu-Feng Zhang
Department of Hepatobiliary Surgery, The First Affiliated Hospital of Xi'an Jiaotong University, 277 West Yanta Road, 710061 Xi'an, Shaanxi, P.R. China
Yi Lv
Department of Hepatobiliary Surgery, The First Affiliated Hospital of Xi'an Jiaotong University, 277 West Yanta Road, 710061 Xi'an, Shaanxi, P.R. China
Yan-Zhen Zheng
Frontier Institute of Science and Technology (FIST), Xi'an Jiaotong University Shenzhen Research School, State Key Laboratory for Mechanical Behavior of Materials, MOE Key Laboratory for Nonequilibrium Synthesis and Modulation of Condensed Matter and School of Chemistry, Xi'an Jiaotong University, 99 Yanxiang Road, Xi'an, Shaanxi, P.R. China; Corresponding author
Summary: Ten lanthanacarborane complexes were synthesized to study the rare B−Hδ−∙∙∙Mn+ inverse hydrogen bonds (IHBs). The average bonding energy of B−Hδ−∙∙∙Ln3+ is theoretically determined to be larger than 24 kJ/mol, which is comparable to moderately strong hydrogen bonds (21–56 kJ/mol). In addition to NMR and IR, magnetometer was used to study the exchange-coupling interaction via such B−Hδ−∙∙∙Ln3+ IHBs in detail, and the coupling constant is determined to be −2.0 cm−1, which is strong enough to compare with single-atom bridged dysprosium(III) complexes. Two imidazolin-iminato incorporated complexes have shown energy barrier for magnetization reversal larger than 1000 K, and the exchange-biasing effects are evident. Moreover, the bonding strengths of B−Hδ−∙∙∙Mn+ IHBs are cation-dependent. If M = Na, the B−Hδ−∙∙∙Na+ bonding energy is reduced to 14 kJ/mol, and the dimerization process is no longer reversible. The exchange-biasing effect is also disappeared. We believe such a finding extends our knowledge of IHBs.
