Computational and Experimental Determination of the Electronic Structure and Optical Properties of Three-Dimensional Zn[M(CN)(4)] Tetracyanates (M = Ni, Pd, and Pt)
Por:
Mojica, Rodrigo, TORRES, ANA ELIZABETH, Lemus-Santana, Ana Adela, Borja-Urby, Rauil, Avila, Yosuan, Reguera, Edilso
Publicada:
3 ago 2023
Ahead of Print:
1 ago 2023
Resumen:
Theelectronic structure of cyanide-based Zn[M(CN)(4)](M = Ni, Pd, and
Pt) coordination polymers is studied by means ofspectroscopic techniques
and DFT-based computational calculations.The observed different &
nu;(CN) band shifts to higher frequencieswhen the inner metal from the
tetracyanate moiety [M(CN)(4)] changes from Ni to Pt and Ni to Pd as a
consequence of the chargedistribution produced by the & pi;
back-bonding phenomena and thecompetition between the polarization
powers from M and Zn. This isevidenced by infrared, Raman, and UV-vis
spectroscopic techniquesin conjunction with hybrid HSE06 calculations.
The sample characterizationwas completed from XPS spectra and HR-TEM
images. The electronic structurewas also studied by the computed
lm-decomposed density of states andband dispersion diagrams. The nature
of the valence band top and conductionband bottom is described by d-M,
p-M, p-nitrogen, and c-carbon hybridizedorbitals. The electronic
behavior of the former solids strongly differsfrom that of the isolated
square-planar tetracyanates, but the HOMO-LUMOelectronic transitions are
still dominated by the tetracyanate [M(CN)(4)] and & pi;-& pi;*
interactions in the three cases.Band gap energy values are reported for
the three studied semiconductors,and the internal metal effect is
analyzed. The indirect nature ofthe electronic transitions associated
with the gap is discussed, andthe values of the effective and reduced
masses are reported.
Filiaciones:
Mojica, Rodrigo:
Inst Politecn Nacl, Ctr Invest Ciencia Aplicada & Tecnol Avanzada, Unidad Legaria, Mexico City 11500, Mexico
TORRES, ANA ELIZABETH:
Univ Nacl Autonoma Mexico, Inst Ciencias Aplicadas & Tecnol, Mexico City 04510, Mexico
Lemus-Santana, Ana Adela:
Inst Politecn Nacl, Ctr Invest Ciencia Aplicada & Tecnol Avanzada, Unidad Legaria, Mexico City 11500, Mexico
Borja-Urby, Rauil:
Inst Politecn Nacl, Ctr Nanociencias & Micro & Nanotecnol CNMN, Mexico City 11500, Mexico
Avila, Yosuan:
Inst Politecn Nacl, Ctr Invest Ciencia Aplicada & Tecnol Avanzada, Unidad Legaria, Mexico City 11500, Mexico
Reguera, Edilso:
Inst Politecn Nacl, Ctr Invest Ciencia Aplicada & Tecnol Avanzada, Unidad Legaria, Mexico City 11500, Mexico
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