In situ Fe K-edge X-ray absorption fine structure of a nitrosyl adduct of iron phthalocyanine irreversibly adsorbed on a high area carbon electrode in an acidic electrolyte.
Key aspects of the microenvironment surrounding the Fe center in the nitrosyl adduct of iron phthalocyanine, [Fe(Pc)(NO)], have been elucidated from the analysis of the Fe K-edge extended X-ray absorption fine structure (EXAFS) of the material adsorbed on the surface of a high area carbon electrode recorded in situ, in 0.5 M H(2)SO(4). Statistical best fits to the EXAFS data place the Fe center in a five-coordinated square pyramidal configuration shifted away from the Pc plane toward the axially bound NO bent at an angle of ca. 40 degrees with respect to the normal to the Pc plane. This environment is analogous to that of Fe in the nitrosyl adduct of crystalline [Fe(TPP)], where TPP = meso-tetraphenylporphyrinato(2-), determined from X-ray diffraction.
Stefan
Ionel C
IC
Department of Chemistry, Case Western Reserve University, Cleveland, Ohio 44106-7078, USA.
Mo
Yibo
Y
Ha
Sung Yong
SY
Kim
Sunghyun
S
Scherson
Daniel A
DA