Preparation and surface photoelectric properties of Fe(II/III) complexes |
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| Institution: | 1. School of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, PR China;2. Institute of Chemistry for Functionalized Materials of Liaoning Normal University, Dalian 116029, PR China;1. Relativistic Molecular Physics group (ReMoPh), Doctorado en Fisicoquímica Molecular, Facultad de Ciencias Exactas, Universidad Andres Bello, República 275, Santiago, Chile;2. Centro de Nanociencias Aplicadas (CANS), Universidad Andres Bello, República 275, Santiago, Chile;1. Moscow State University, Chemical Department, Leninskie Gory 11, Moscow 119991, Russia;2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, Moscow 119991, Russia;3. National Research Center “Kurchatov Institute”, Moscow, Russia;4. Peoples'' Friendship University of Russia (RUDN), Moscow, Russia |
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| Abstract: | Four Fe(II/III) supramolecules, {Fe(Hpdc)2(H2O)2]·2H2O} (1), Fe(HImbc)2(H2O)2] (2), Fe(phen)2(CN)2]·CH3CH2OH·2H2O (3), KFe(tp)2]·SO4 (4) (H2pdc = 2,5-Pyridinedicarboxylic acid, H2Imbc = 4,5-Imidazoledicarboxylic acid, phen = 1,10-phenanthroline, tp− = poly(pyrazolyl)borate), were synthesized by hydrothermal and room temperature stirring methods. They were characterized by single crystal X-ray diffraction, surface photovoltage spectroscopy (SPS), field-induced surface photovoltage spectroscopy (FISPS), electron paramagnetic resonance (EPR), UV–Vis absorption spectra (UV–Vis), infrared spectra (IR) and element analysis. The structural analyses indicate that complex (1) is a supramolecule with 2D structure connected by hydrogen bonds. Complex (2) is a supramolecule with hydrogen-bonded 3D structure. Complexes (3) and (4) are both 1D supramolecules connected by hydrogen bonds. The electronic state of central metal Fe(II) ions in complexes (1) and (2) is d6 with FeN2O4 coordination mode, lying in weaker distorted octahedral field. The electronic state of Fe(II) ion in complex (3) is d6 with Fe(CN)2N4 mode in the strong distorted octahedral field. The electronic state of Fe(III) ion in complex (4) is d5 with FeN6 mode, lying in the strong octahedral field. The micro-environment of Fe(II/III) ions in the four complexes is further investigated by EPR. The SPS of four complexes all exhibit photovoltage responses in the range of 300–700 nm. This indicates that they all possess certain photoelectric conversion capability. The effects of component, structure, type of ligands of the complexes, valence state and coordination micro-environment of the central metal ions on the SPS were discussed. Furthermore, the SPS and UV–Vis absorption spectra were interrelated. |
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