Electronic Transitions in Methyl Fluoride and in Fluoroform1

This contribution presents the results of the TD-DFT and CASSCF/CASPT2 calculations on [W(CO)4(MeDAB)] (MeDAB = N,N'-dimethyl-1,4-diazabutadiene), [W(CO)4(en)] (en = ethylenediamine), [W(CO)5(py)] (py = pyridine) and [W(CO)5(CNpy)] (CNpy = 4-cyanopyridine) complexes. Contrary to the textbook interpretation, calculations on the model complex [W(CO)4(MeDAB)] and [W(CO)5(CNpy)] show that the lowest W→MeDAB and W→CNpy MLCT excited states are immediately followed in energy by several W→CO MLCT states, instead of ligand-field (LF) states. The lowest-lying excited states of [W(CO)4(en)] system were characterized as W(COeq)2→COax CT excitations, which involve a remarkable electron density redistribution between axial and equatorial CO ligands. [W(CO)5(py)] possesses closely-lying W→CO and W→py MLCT excited states. The calculated energies of these states are sensitive to the computational methodology used and can be easily influenced by a substitution effect. The calculated shifts of [W(CO)4(en)] stretching CO frequencies due to excitation are in agreement with picosecond time-resolved infrared spectroscopy experiments and confirm the occurrence of low-lying M→CO MLCT transitions. No LF electronic transitions were found for either of the complexes studied in the region up to 4 eV.

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Tuning of Electronic Properties in Conducting Polymers

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20011208 ◽

2001 ◽

Vol 66 (8) ◽

pp. 1208-1218 ◽

Cited By ~ 3

Author(s):

Guofeng Li ◽

Mira Josowicz ◽

Jiří Janata

Keyword(s):

Hydrogen Bonding ◽

Binding Site ◽

Binding Sites ◽

Polymer Chains ◽

Electronic Transitions ◽

Weakly Bound ◽

Ordered Structures ◽

Doped Polymer ◽

Positively Charged ◽

Repeated Cycling

Structural and electronic transitions in poly(thiophenyleneiminophenylene), usually referred to as poly(phenylenesulfidephenyleneamine) (PPSA) upon electrochemical doping with LiClO4 have been investigated. The unusual electrochemical behavior of PPSA indicates that the dopant anions are bound in two energetically different sites. In the so-called "binding site", the ClO4- anion is Coulombically attracted to the positively charged S or N sites on one chain and simultaneously hydrogen-bonded with the N-H group on a neighboring polymer chain. This strong interaction causes a re-organization of the polymer chains, resulting in the formation of a networked structure linked together by these ClO4- Coulombic/hydrogen bonding "bridges". However, in the "non-binding site", the ClO4- anion is very weakly bound, involves only the electrostatic interaction and can be reversibly exchanged when the doped polymer is reduced. In the repeated cycling, the continuous and alternating influx and expulsion of ClO4- ions serves as a self-organizing process for such networked structures, giving rise to a diminishing number of available "non-binding" sites. The occurrence of these ordered structures has a major impact on the electrochemical activity and the morphology of the doped polymer. Also due to stabilization of the dopant ions, the doped polymer can be kept in a stable and desirable oxidation state, thus both work function and conductivity of the polymer can be electrochemically controlled.

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