signature=de4fefc549f99f0b0c76a2cec8e340bf,Magnetic-field-induced modifications of the electronic st...

【摘要】

Ni(en)_2NO_2BF_4 (NENB) is isostructural to Ni(en)_2NO_2ClO_4, the well-known Haldane compound. We have measured the near infrared and visible frequency polarized transmittances of NENB as a function of temperature from 6 to 300 K and in magnetic fields (H) up to 30 T. We identify near infrared spin-allowed and spin-forbidden (SF) d-d excitations of the Ni~(2+) ion as well as a Ni~(2+)-to-NO_2~- charge-transfer (CT) transition at 2.5 eV, confirmed by vibrational fine structure on the CT band due to the nitrite ion. The spin-allowed d-d bands exhibit temperature dependence consistent with vibronic transitions. The spin-forbidden and electron transfer transitions are noticeably sensitive to magnetic field. Above H ≈ 10 T, the NENB SF excitation is linearly suppressed by field, whereas the CT transition intensity increases; the onset field agrees with that observed in the high-field magnetization. For comparison, we made the same measurements on a compound having similar near infrared electronic transitions but a different magnetic ground state: the paramagnetic material Ni(en)_3(ClO_4)_2·H_2O (NEN3P). The SF bands of NENB are relatively more intense than those of NEN3P, suggesting that a spin exchange mechanism enhances their intensity in NENB, in contrast to activation solely by spin-orbit coupling in NEN3P. The H dependence of the SF band also differs in the two materials; in NEN3P, suppression of the SF intensity commences at H≈0 T. In general, the contrasting behaviors of field-sensitive excitations in the Haldane and paramagnetic analog compounds reveal a correlation between the electronic structure and magnetic properties.