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Un modelo de tres estados para el polimorfismo en compuestos lineales de tricobalto.

Dimitrios A Pantazis¹, John E McGrady

¹WestCHEM, Department of Chemistry, University of Glasgow, Glasgow G12 8QQ, United Kingdom.

Journal of the American Chemical Society

|March 23, 2006

Resumen

Los compuestos polimórficos de tricobalto exhiben estados electrónicos distintos, lo que lleva a cambios estructurales. El cruce de espín dependiente de la temperatura en estos complejos de cobalto influye en las longitudes de enlace y las configuraciones electrónicas.

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Área de la Ciencia:

Química Inorgánica La Química Inorgánica es la química inorgánica.
Química del estado sólido.
Ciencia de los materiales Ciencia de los materiales.

Sus antecedentes:

Los compuestos de tricobalto como el Co3 ((mu3-dpa) 4Cl2 y el Co3 ((mu3-dpa) 4Br2 muestran un polimorfismo significativo.
Comprender los estados electrónicos que gobiernan estas variaciones estructurales es crucial.

Objetivo del estudio:

Para dilucidar el comportamiento polimórfico de los compuestos lineales de tricobalto.
Para explicar las transiciones estructurales utilizando un modelo de estados electrónicos distintos.

Principales métodos:

Modelado teórico de los estados electrónicos.
Análisis de los cambios estructurales dependientes de la temperatura.
Investigación de los fenómenos de cruce de espín.

Principales resultados:

Un modelo de tres estados electrónicos explica el polimorfismo observado.
Las altas temperaturas involucran a la población de los estados de doble (2A) y cuarteto (4B).
Las bajas temperaturas inducen el cruce de espín a un estado doble único (2B) con carácter orbital distribuido d(x2-y2).

Conclusiones:

El modelo de estructura electrónica explica con éxito el polimorfismo impulsado por la temperatura.
El cruce de espín y la distribución de caracteres orbitales son claves para comprender los cambios estructurales.
La población variable de orbitales de cobalto conduce a cambios continuos en las longitudes de enlace.