Analytical Sciences

Extended X-ray Absorption Fine Structure of Copper(II) Complexes at the Air-Water Interface by a Polarized Total-Reflection X-ray Absorption Technique

Hirohisa NAGATANI,* Hajime TANIDA,** Iwao WATANABE,*** and Takamasa SAGARA*

*Department of Applied Chemistry, Faculty of Engineering, Nagasaki University, Bunkyo, Nagasaki 852-8521, Japan
**Materials Science Division, Japan Synchrotron Radiation Research Institute, Kouto, Sayo, Hyogo 679-5198, Japan
***SR Center, Ritsumeikan University, Noji-Higashi, Kusatsu, Shiga 525-8577, Japan

Copper(II) complexes spread on an aqueous solution surface were studied by a polarized total-reflection X-ray absorption fine structure (TR-XAFS) technique. The polarized TR-XAFS spectra at the Cu-K edge for copper(II) porphyrins and copper(II) chlorophyllin in a monolayer were measured in situ at the air-water interface. The polarization dependences of X-ray absorption near-edge structure (XANES) involving a 1s→4p_z transition allowed us to estimate the molecular orientation and the local coordination structure around the copper(II) atom in the polarization plane selectively. The extended X-ray absorption fine structure (EXAFS) region of the polarized TR-XAFS spectra for the metal complexes present at the air-water interface was successfully analyzed for the first time. The relative coordination number for the copper center evaluated from the EXAFS analysis indicated larger values in the vertical polarization than in the horizontal one, in agreement with the standing-up molecular orientation at the air-water interface estimated from the XANES region.

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