Abstract
By tailoring the chemistry of the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (bodipy) core in order to change its spectroscopic properties, we linked some modified bodipy dyes to Pt(ii)-terpyridine centers thereby preparing three novel hybrid complexes. In one of such species, two pyrene subunits are also present. The absorption spectra and luminescence properties (both at room temperature in acetonitrile solution and at 77 K in butyronitrile rigid matrix) of the new hybrid complexes and of their bodipy parent species have been investigated, and compared with those of previously studied compounds. Absorption spectra showed that the different chromophoric subunits roughly keep their own features in the multicomponent systems, indicating the supramolecular nature of the compounds. Efficient photoinduced intercomponent energy transfer takes place in the various hybrid Pt(ii)-terpyridine-bodipy compounds, by taking advantage of different mechanisms: at room temperature in fluid solution very efficient energy transfer from the 3MLCT state(s) of the Pt residue to the lowest-lying 3bodipy is mediated by a charge transfer state via a two-step electron transfer process. Direct energy transfer from 3MLCT state(s) to the 3bodipy states takes place at 77 K, most likely via the Dexter mechanism. When two pyrene fragments are grafted to the boron, cascade energy transfer from the pyrene to the 1bodipy also occurs by the Förster mechanism. For one of the new compounds, 3bodipy emission with a maximum at 738 nm is also observed at cryogenic temperature.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 7392-7402 |
| Number of pages | 11 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 12 |
| Issue number | 27 |
| DOIs | |
| State | Published - Jan 1 2010 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
Cite this
Hybrid complexes : Pt(ii)-terpyridine linked to various acetylide-bodipy subunits. / Nastasi, Francesco; Puntoriero, Fausto; Campagna, Sebastiano; Olivier, Jean-Hubert; Ziessel, Raymond.
In: Physical Chemistry Chemical Physics, Vol. 12, No. 27, 01.01.2010, p. 7392-7402.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Hybrid complexes
T2 - Pt(ii)-terpyridine linked to various acetylide-bodipy subunits
AU - Nastasi, Francesco
AU - Puntoriero, Fausto
AU - Campagna, Sebastiano
AU - Olivier, Jean-Hubert
AU - Ziessel, Raymond
PY - 2010/1/1
Y1 - 2010/1/1
N2 - By tailoring the chemistry of the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (bodipy) core in order to change its spectroscopic properties, we linked some modified bodipy dyes to Pt(ii)-terpyridine centers thereby preparing three novel hybrid complexes. In one of such species, two pyrene subunits are also present. The absorption spectra and luminescence properties (both at room temperature in acetonitrile solution and at 77 K in butyronitrile rigid matrix) of the new hybrid complexes and of their bodipy parent species have been investigated, and compared with those of previously studied compounds. Absorption spectra showed that the different chromophoric subunits roughly keep their own features in the multicomponent systems, indicating the supramolecular nature of the compounds. Efficient photoinduced intercomponent energy transfer takes place in the various hybrid Pt(ii)-terpyridine-bodipy compounds, by taking advantage of different mechanisms: at room temperature in fluid solution very efficient energy transfer from the 3MLCT state(s) of the Pt residue to the lowest-lying 3bodipy is mediated by a charge transfer state via a two-step electron transfer process. Direct energy transfer from 3MLCT state(s) to the 3bodipy states takes place at 77 K, most likely via the Dexter mechanism. When two pyrene fragments are grafted to the boron, cascade energy transfer from the pyrene to the 1bodipy also occurs by the Förster mechanism. For one of the new compounds, 3bodipy emission with a maximum at 738 nm is also observed at cryogenic temperature.
AB - By tailoring the chemistry of the 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (bodipy) core in order to change its spectroscopic properties, we linked some modified bodipy dyes to Pt(ii)-terpyridine centers thereby preparing three novel hybrid complexes. In one of such species, two pyrene subunits are also present. The absorption spectra and luminescence properties (both at room temperature in acetonitrile solution and at 77 K in butyronitrile rigid matrix) of the new hybrid complexes and of their bodipy parent species have been investigated, and compared with those of previously studied compounds. Absorption spectra showed that the different chromophoric subunits roughly keep their own features in the multicomponent systems, indicating the supramolecular nature of the compounds. Efficient photoinduced intercomponent energy transfer takes place in the various hybrid Pt(ii)-terpyridine-bodipy compounds, by taking advantage of different mechanisms: at room temperature in fluid solution very efficient energy transfer from the 3MLCT state(s) of the Pt residue to the lowest-lying 3bodipy is mediated by a charge transfer state via a two-step electron transfer process. Direct energy transfer from 3MLCT state(s) to the 3bodipy states takes place at 77 K, most likely via the Dexter mechanism. When two pyrene fragments are grafted to the boron, cascade energy transfer from the pyrene to the 1bodipy also occurs by the Förster mechanism. For one of the new compounds, 3bodipy emission with a maximum at 738 nm is also observed at cryogenic temperature.
UR - http://www.scopus.com/inward/record.url?scp=77954322604&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=77954322604&partnerID=8YFLogxK
U2 - 10.1039/c003789c
DO - 10.1039/c003789c
M3 - Article
C2 - 20532400
AN - SCOPUS:77954322604
VL - 12
SP - 7392
EP - 7402
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 27
ER -