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A study of cation-dependent inverse hydrogen bonds and magnetic exchange-couplings in lanthanacarborane complexes.

ABSTRACT: Ten lanthanacarborane complexes were synthesized to study the rare B-H^δ-∙∙∙Mⁿ⁺ inverse hydrogen bonds (IHBs). The average bonding energy of B-H^δ-∙∙∙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-H^δ-∙∙∙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-H^δ-∙∙∙Mⁿ⁺ IHBs are cation-dependent. If M = Na, the B-H^δ-∙∙∙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.

SUBMITTER: Jin PB

PROVIDER: S-EPMC8271178 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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A study of cation-dependent inverse hydrogen bonds and magnetic exchange-couplings in lanthanacarborane complexes.

Jin Peng-Bo PB Luo Qian-Cheng QC Zhai Yuan-Qi YQ Wang Yi-Dian YD Ma Yan Y Tian Lei L Zhang Xinliang X Ke Chao C Zhang Xu-Feng XF Lv Yi Y Zheng Yan-Zhen YZ

iScience 20210619 7

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 const ...[more]

PMID: 34278267

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Project description:Multicenter transition-metal complexes (MCTMs) with magnetically interacting ions have been proposed as components for information-processing devices and storage units. For any practical application of MCTMs as magnetic units, it is crucial to characterize their magnetic behavior, and in particular, the isotropic magnetic exchange coupling, J, between its magnetic centers. Due to the large size of typical MCTMs, density functional theory is the only practical electronic structure method for evaluating the J coupling. Here, we assess the accuracy of different density functional approximations for predicting the magnetic couplings of eight dinuclear transition-metal complexes, including five dimanganese, two dicopper, and one divanadium with known reliable experimental J couplings spanning from ferromagnetic to strong antiferromagnetic. The density functionals considered include global hybrid functionals which mix semilocal density functional approximations and exact exchange with a fixed admixing parameter, six local hybrid functionals where the admixing parameters are extended to be spatially dependent, the SCAN and r2SCAN meta-generalized gradient approximations (GGAs), and two widely used GGAs. We found that global hybrids tested in this work have a tendency to over-correct the error in magnetic coupling parameters from the Perdew-Burke-Ernzerhof (PBE) GGA as seen for manganese complexes. The performance of local hybrid density functionals shows no improvement in terms of bias and is scattered without a clear trend, suggesting that more efforts are needed for the extension from global to local hybrid density functionals for this particular property. The SCAN and r2SCAN meta-GGAs are found to perform as well as benchmark global hybrids on most tested complexes. We further analyze the charge density redistribution of meta-GGAs as well as global and local hybrid density functionals with respect to that of PBE, in connection to the self-interaction error or delocalization error.

Dataset Information

A study of cation-dependent inverse hydrogen bonds and magnetic exchange-couplings in lanthanacarborane complexes.

Publications

A study of cation-dependent inverse hydrogen bonds and magnetic exchange-couplings in lanthanacarborane complexes.

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