Ultrafast excited-state dynamics of rhenium(I) photosensitizers [Re(Cl)(CO)3(N,N)] and [Re(imidazole)(CO)3(N,N)]+: diimine effects
Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence up-conversion, transient absorption in the 650-285 nm range (using broad-band UV probe pulses arou...
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| Published in: | Inorganic chemistry Vol. 50; no. 7; p. 2932 |
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| Main Authors: | , , , , , , , , , , |
| Format: | Journal Article |
| Language: | English |
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04.04.2011
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| ISSN: | 1520-510X |
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| Abstract | Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence up-conversion, transient absorption in the 650-285 nm range (using broad-band UV probe pulses around 300 nm) and picosecond time-resolved IR (TRIR) spectroscopy in the region of CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing to at least two hot triplet states with a rate that is faster in Cl (∼100 fs)(-1) than in imidazole (∼150 fs)(-1) complexes but essentially independent of the N,N ligand. TRIR spectra indicate the presence of two long-lived triplet states that are populated simultaneously and equilibrate in a few picoseconds. The minor state accounts for less than 20% of the relaxed excited population. UV-vis transient spectra were assigned using open-shell time-dependent density functional theory calculations on the lowest triplet CT state. Visible excited-state absorption originates mostly from mixed L;N,N(•-) → Re(II) ligand-to-metal CT transitions. Excited bpy complexes show the characteristic sharp near-UV band (Cl, 373 nm; imH, 365 nm) due to two predominantly ππ*(bpy(•-)) transitions. For phen and dmp, the UV excited-state absorption occurs at ∼305 nm, originating from a series of mixed ππ* and Re → CO;N,N(•-) MLCT transitions. UV-vis transient absorption features exhibit small intensity- and band-shape changes occurring with several lifetimes in the 1-5 ps range, while TRIR bands show small intensity changes (≤5 ps) and shifts (∼1 and 6-10 ps) to higher wavenumbers. These spectral changes are attributable to convoluted electronic and vibrational relaxation steps and equilibration between the two lowest triplets. Still slower changes (≥15 ps), manifested mostly by the excited-state UV band, probably involve local-solvent restructuring. Implications of the observed excited-state behavior for the development and use of Re-based sensitizers and probes are discussed. |
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| AbstractList | Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence up-conversion, transient absorption in the 650-285 nm range (using broad-band UV probe pulses around 300 nm) and picosecond time-resolved IR (TRIR) spectroscopy in the region of CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing to at least two hot triplet states with a rate that is faster in Cl (∼100 fs)(-1) than in imidazole (∼150 fs)(-1) complexes but essentially independent of the N,N ligand. TRIR spectra indicate the presence of two long-lived triplet states that are populated simultaneously and equilibrate in a few picoseconds. The minor state accounts for less than 20% of the relaxed excited population. UV-vis transient spectra were assigned using open-shell time-dependent density functional theory calculations on the lowest triplet CT state. Visible excited-state absorption originates mostly from mixed L;N,N(•-) → Re(II) ligand-to-metal CT transitions. Excited bpy complexes show the characteristic sharp near-UV band (Cl, 373 nm; imH, 365 nm) due to two predominantly ππ*(bpy(•-)) transitions. For phen and dmp, the UV excited-state absorption occurs at ∼305 nm, originating from a series of mixed ππ* and Re → CO;N,N(•-) MLCT transitions. UV-vis transient absorption features exhibit small intensity- and band-shape changes occurring with several lifetimes in the 1-5 ps range, while TRIR bands show small intensity changes (≤5 ps) and shifts (∼1 and 6-10 ps) to higher wavenumbers. These spectral changes are attributable to convoluted electronic and vibrational relaxation steps and equilibration between the two lowest triplets. Still slower changes (≥15 ps), manifested mostly by the excited-state UV band, probably involve local-solvent restructuring. Implications of the observed excited-state behavior for the development and use of Re-based sensitizers and probes are discussed. |
| Author | Chergui, Majed Lancaster, Kyle M Clark, Ian P Zális, Stanislav Vlcek, Jr, Antonín Blanco-Rodríguez, Ana María Braem, Olivier Cannizzo, Andrea Towrie, Michael El Nahhas, Amal Consani, Cristina |
| Author_xml | – sequence: 1 givenname: Amal surname: El Nahhas fullname: El Nahhas, Amal organization: Laboratoire de Spectroscopie Ultrarapide, ISIC, FSB-BSP, Ecole Polytechnique Fédérale de Lausanne, Lausanne-Dorigny, Switzerland – sequence: 2 givenname: Cristina surname: Consani fullname: Consani, Cristina – sequence: 3 givenname: Ana María surname: Blanco-Rodríguez fullname: Blanco-Rodríguez, Ana María – sequence: 4 givenname: Kyle M surname: Lancaster fullname: Lancaster, Kyle M – sequence: 5 givenname: Olivier surname: Braem fullname: Braem, Olivier – sequence: 6 givenname: Andrea surname: Cannizzo fullname: Cannizzo, Andrea – sequence: 7 givenname: Michael surname: Towrie fullname: Towrie, Michael – sequence: 8 givenname: Ian P surname: Clark fullname: Clark, Ian P – sequence: 9 givenname: Stanislav surname: Zális fullname: Zális, Stanislav – sequence: 10 givenname: Majed surname: Chergui fullname: Chergui, Majed – sequence: 11 givenname: Antonín surname: Vlcek, Jr fullname: Vlcek, Jr, Antonín |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/21388162$$D View this record in MEDLINE/PubMed |
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| Snippet | Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n... |
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| SubjectTerms | Imines - chemistry Molecular Conformation Organometallic Compounds - chemistry Photosensitizing Agents - chemistry Quantum Theory Rhenium - chemistry Ultraviolet Rays |
| Title | Ultrafast excited-state dynamics of rhenium(I) photosensitizers [Re(Cl)(CO)3(N,N)] and [Re(imidazole)(CO)3(N,N)]+: diimine effects |
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