Structure, Physical and Photophysical Properties, and Charge Separation Studies of Re(bpm)(CO)3Ln+ Complexes (L = CH3CN, py, MeQ+, py-PTZ)
| Autor: | Marc W. Perkovic, R.J. Shaver, D.P. Rillema, Clifton Woods |
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| Rok vydání: | 1995 |
| Předmět: | |
| Zdroj: | Inorganic Chemistry. 34:5446-5454 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic00126a013 |
| Popis: | The synthesis, structure, and physical and/or photophysical properties of Re(bpm)(CO){sub 3}L{sup n+}, where bpm is 2,2{prime}- bipyrimidine and L = CH{sub 3}CN, py (pyridine), MeQ{sup +} (N-methyl-r,r{prime}-bipyridinium ion), and py-PTZ (10-(4-picolyl)- phenothiazine), are described. The structure of [Re(bpm)(CO){sub 3}(CH{sub 3}CN)]PF{sub 6}{center_dot}1/2 CH{sub 3}CN was determined by single-crystal X-ray diffraction. It crystallized in the space group P1 with cell dimensions a = 10.089(11) {Angstrom}, b = 11.855(6) {Angstrom}, c = 18.990(6) {Angstrom}, {alpha} = 89.71(3){degrees}, {beta} = 77.66(6){degrees}, {gamma} = 65.83(6){degrees}, Z =4, and D{sub calcd} = 2.082 g/cm{sup 3}. Of the 5565 reflections (Mo K{alpha}, 3.5{degrees} {le} 2{theta} {le} 45{degrees}), 4721 reflections with F{sub o} {ge} 3.0{sigma}(F{sub o}) were used in full-matrix least-squares refinement. Final residuals were R(F)=0.0692 and R{sub w}(F)=0.1026. The asymmetric unit contained two independent cations. The Re-N(bpm) bond distances were 2.171(9) and 2.198(10) {Angstrom} for one cation and 2.161(12) and 2.187(12) {Angstrom} for the other; the two Re-N(CH{sub 3}CN) bond distances were 2.094(14) and 2.177(13) {Angstrom}, and the Re-C(CO) bond distances were 1.908(15), 1.938(17), and 1.912(12) {Angstrom} for the first cation and 1.897(15), 1.896(19), and 1.919(15) {Angstrom} for the second. The complexes exhibited three CO infrared-active bands in the 1900-2100 cm{sup {minus}1} region and underwent optical transitionsmore » in the 300-350 nm region assigned to d{pi}(Re) {r_arrow} {pi}*(bpm) transitions and in the 200-300 nm region assigned to intraligand {pi} {r_arrow} {pi}* transitions. The complexes underwent multiple reductions attributed to reduction of coordinated bpm and MeQ{sup +}.« less |
| Databáze: | OpenAIRE |
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