Evidence for surface effects on the intermolecular interactions in Fe(II) spin crossover coordination polymers.

From X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS), it is evident that the spin state transition behavior of Fe(II) spin crossover coordination polymer crystallites at the surface differs from the bulk. A comparison of four different coordination polymers reveals that the observed surface properties may differ from bulk for a variety of reasons. There are Fe(II) spin crossover coordination polymers with either almost complete switching of the spin state at the surface or no switching at all. Oxidation, differences in surface packing, and changes in coordination could all contribute to making the surface very different from the bulk. Some Fe(II) spin crossover coordination polymers may be sufficiently photoactive so that X-ray spectroscopies cannot discern the spin state transition.

Coordination Chemistry of Uranyl Ions with Surface-Immobilized Peptides: An XPS Study.

The coordination chemistry of uranyl ions with surface immobilized peptides was studied using X-ray photoemission spectroscopy (XPS). All the peptides in the study were modified using a six-carbon alkanethiol as a linker on a gold substrate with methylene blue as the redox label. The X-ray photoemission spectra reveal that each modified peptide interacts differently with the uranyl ion. For all the modified peptides, the XPS spectra were taken in both the absence and presence of the uranium, and their comparison reveals that the interaction depends on the chemical group present in the peptides. The XPS results show that, among all the modified peptides in the current study, the (arginine)9 (R9) modified peptide showed the largest response to uranium. In the order of response to uranium, the second largest response was shown by the modified (arginine)6 (R6) peptide followed by the modified (lysine)6 (K6) peptide. Other modified peptides, (alanine)6 (A6), (glutamic acid)6 (E6) and (serine)6 (S6), did not show any response to uranium.

Electronic structure of cobalt valence tautomeric molecules in different environments.

Future molecular microelectronics require the electronic conductivity of the device to be tunable without impairing the voltage control of the molecular electronic properties. This work reports the influence of an interface between a semiconducting polyaniline polymer or a polar poly-D-lysine molecular film and one of two valence tautomeric complexes, i.e., [CoIII(SQ)(Cat)(4-CN-py)2] ↔ [CoII(SQ)2(4-CN-py)2] and [CoIII(SQ)(Cat)(3-tpp)2] ↔ [CoII(SQ)2(3-tpp)2]. The electronic transitions and orbitals are identified using X-ray photoemission, X-ray absorption, inverse photoemission, and optical absorption spectroscopy measurements that are guided by density functional theory. Except for slightly modified binding energies and shifted orbital levels, the choice of the underlying substrate layer has little effect on the electronic structure. A prominent unoccupied ligand-to-metal charge transfer state exists in [CoIII(SQ)(Cat)(3-tpp)2] ↔ [CoII(SQ)2(3-tpp)2] that is virtually insensitive to the interface between the polymer and tautomeric complexes in the CoII high-spin state.

Voltage controlled bio-organic inverse phototransistor.

Thin films of poly-d-lysine act as polar organic and are also light sensitive. The capacitance-voltage, current-voltage, and transistor behavior were studied to gauge the photoresponse of possible poly-d-lysine thin film devices both with and without methylene blue as an additive. Transistors fabricated from poly-d-lysine act as inverse phototransistors, i.e., the on-state current is greatest in the absence of illumination. The poly-d-lysine thin film capacitance and the transistor current decrease with illumination, both with and without methylene blue as an additive. This suggests that the unbinding of photo exciton is significantly hindered in this system which is supported by the significant charge carrier lifetime for poly-d-lysine films both with and without methylene blue. For the majority carrier, the transistor geometry appears to depend on the gate voltage; in other words, the majority carrier depends on the polarization of the poly-d-lysine films, both with and without methylene blue as an additive.

Evidence of dynamical effects and critical field in a cobalt spin crossover complex.

The [Co(SQ)2(4-CN-py)2] complex exhibits dynamical effects over a wide range of temperature. The orbital moment, determined by X-ray magnetic circular dichroism (XMCD) with decreasing applied magnetic field, indicates a nonzero critical field for net alignment of magnetic moments, an effect not seen with the spin moment of [Co(SQ)2(4-CN-py)2].