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Issue 9, 2012
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Photophysical properties of 4,4′-di-tert-butyl-2,2′-bipyridine supported 6-membered 2,2′-diphenyl-X platinacycles (X = CH2, NMe, O)

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Abstract

The six-membered platinacycle complex, Pt(tBu2bpy)(C6H4OC6H4) (6) (tBu2bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) has been prepared from Pt(tBu2bpy)Cl2 and 2,2′-dilithio-diphenyl ether. Platinacycle 6 and its analogs with X = CH2 (4) and NMe (5) exhibit intense solid-state photoluminescence and nearly identical crystal structures. The photophysical properties of 4–6 in the visible range are dominated by mixed metal–ligand-to-ligand charge transfer (MLL′CT) transitions involving high-lying filled mixed metal–ligand orbitals (ML), composed primarily of platinacyclic ring-based d- and π-orbitals, and a low lying vacant π* orbital (L′) of the tBu2bpy ligand. Lone pair donation from the bridging oxygen atom and especially the NMe group increases the energy of the mixed metal–ligand orbital (ML) without altering the energy of the tBu2bpy π* orbital. As a result, the MLL′CT state energy decreases and the absorption and emission wavelengths are red-shifted. DFT and TD-DFT calculations support the experimental results. Additional calculations on the unknown platinacycles with X = CO (7) and SO2 (8) predict a blue-shift for the MLL′CT absorption and emission. Two nearly equal energy triplet minima were located on the DFT triplet surface for 4–6. One of these (4T–6T) has a geometry very similar to the ground-state singlet (as represented by 4–6) and is associated with the emissive 3MLL′CT excited state. The other triplet-state (4T′–6T′) has a distorted structure where the platinacycle ring is twisted out of the Pt(tBu2bpy) plane. Thermal access to this distorted triplet may be responsible for the loss of photoluminescence in room temperature solutions of 4–6.

Graphical abstract: Photophysical properties of 4,4′-di-tert-butyl-2,2′-bipyridine supported 6-membered 2,2′-diphenyl-X platinacycles (X = CH2, NMe, O)

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Publication details

The article was received on 24 Aug 2011, accepted on 06 Dec 2011 and first published on 19 Jan 2012


Article type: Paper
DOI: 10.1039/C2DT11594H
Dalton Trans., 2012,41, 2601-2611

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    Photophysical properties of 4,4′-di-tert-butyl-2,2′-bipyridine supported 6-membered 2,2′-diphenyl-X platinacycles (X = CH2, NMe, O)

    R. Robinson, A. R. Karikachery and P. R. Sharp, Dalton Trans., 2012, 41, 2601
    DOI: 10.1039/C2DT11594H

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