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Article: Electronic spectra and photophysics of platinum(II) complexes with α-diimine ligands. Mixed complexes with halide ligands
Title | Electronic spectra and photophysics of platinum(II) complexes with α-diimine ligands. Mixed complexes with halide ligands |
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Authors | |
Issue Date | 1993 |
Publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic |
Citation | Inorganic Chemistry, 1993, v. 32 n. 11, p. 2518-2524 How to Cite? |
Abstract | Emission properties have been studied for a series of compounds of the formula (L2)PtCl2, where L2 is N,N,N′,N′-tetramethylethylenediamine, 2,2′-bipyridine (bpy), 4,4′-Me2bpy, 5,5′-Me2bpy, 4,4′-(t-Bu)2bpy, 3,3′-(CH3OCO)2bpy, and 1,10-phenanthroline, and also for the compound Pt(bpy)I2. Most of them exhibit orange to red luminescence from a triplet ligand-field (3LF) state, both as solids and in glassy solution. These emissions are very broad (fwhm 2300-3400 cm-1 at 10 K) and structureless and are strongly Stokes-shifted from absorption. The two exceptions are the solid "red" form of Pt(bpy)Cl2, which exhibits a relatively narrow (fwhm 1050 cm-1 at 10 K), vibronically structured (Δν ∼ 1500 cm-1) red emission, and Pt(3,3′-(CH3OCO)2bpy)Cl2, which exhibits a broad (fwhm 2500 cm-1 at 10 K) but structured (Δν ∼ 1300 cm-1) orange emission. Both of these emissions are assigned to triplet metal-to-ligand charge-transfer (3MLCT) excited states. For the former compound, a linear-chain structure has destabilized a dσ*(dz2) level, yielding a dσ* → π*(bpy) state as the lowest energy excited state, while for the latter, the strongly electron-withdrawing substituents have stabilized a bpy π* level, yielding a dxz,yz → π*(bpy) state as the lowest energy excited state. The relative energies of the various types of excited states, including ligand 3ππ* states, are discussed in detail. The crystal structures of Pt(5,5′-Me2bpy)Cl2 (monoclinic Cc, Z = 4, a = 13.413(7) Å, b = 9.063(4) Å, c = 12.261(9) Å, β = 121.71(6)°) and Pt(3,3′-(CH3OCO)2bpy)Cl2 (triclinic P1, Z = 2, a = 7.288(2) Å, b = 9.932(3) Å, c = 11.881(5) Å, α = 98.04(3)°, β = 103.56(3)°, γ = 106.54(3)°) are reported. © 1993 American Chemical Society. |
Persistent Identifier | http://hdl.handle.net/10722/168074 |
ISSN | 2023 Impact Factor: 4.3 2023 SCImago Journal Rankings: 0.928 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Miskowski, VM | en_US |
dc.contributor.author | Houlding, VH | en_US |
dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Wang, Y | en_US |
dc.date.accessioned | 2012-10-08T03:14:50Z | - |
dc.date.available | 2012-10-08T03:14:50Z | - |
dc.date.issued | 1993 | en_US |
dc.identifier.citation | Inorganic Chemistry, 1993, v. 32 n. 11, p. 2518-2524 | en_US |
dc.identifier.issn | 0020-1669 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168074 | - |
dc.description.abstract | Emission properties have been studied for a series of compounds of the formula (L2)PtCl2, where L2 is N,N,N′,N′-tetramethylethylenediamine, 2,2′-bipyridine (bpy), 4,4′-Me2bpy, 5,5′-Me2bpy, 4,4′-(t-Bu)2bpy, 3,3′-(CH3OCO)2bpy, and 1,10-phenanthroline, and also for the compound Pt(bpy)I2. Most of them exhibit orange to red luminescence from a triplet ligand-field (3LF) state, both as solids and in glassy solution. These emissions are very broad (fwhm 2300-3400 cm-1 at 10 K) and structureless and are strongly Stokes-shifted from absorption. The two exceptions are the solid "red" form of Pt(bpy)Cl2, which exhibits a relatively narrow (fwhm 1050 cm-1 at 10 K), vibronically structured (Δν ∼ 1500 cm-1) red emission, and Pt(3,3′-(CH3OCO)2bpy)Cl2, which exhibits a broad (fwhm 2500 cm-1 at 10 K) but structured (Δν ∼ 1300 cm-1) orange emission. Both of these emissions are assigned to triplet metal-to-ligand charge-transfer (3MLCT) excited states. For the former compound, a linear-chain structure has destabilized a dσ*(dz2) level, yielding a dσ* → π*(bpy) state as the lowest energy excited state, while for the latter, the strongly electron-withdrawing substituents have stabilized a bpy π* level, yielding a dxz,yz → π*(bpy) state as the lowest energy excited state. The relative energies of the various types of excited states, including ligand 3ππ* states, are discussed in detail. The crystal structures of Pt(5,5′-Me2bpy)Cl2 (monoclinic Cc, Z = 4, a = 13.413(7) Å, b = 9.063(4) Å, c = 12.261(9) Å, β = 121.71(6)°) and Pt(3,3′-(CH3OCO)2bpy)Cl2 (triclinic P1, Z = 2, a = 7.288(2) Å, b = 9.932(3) Å, c = 11.881(5) Å, α = 98.04(3)°, β = 103.56(3)°, γ = 106.54(3)°) are reported. © 1993 American Chemical Society. | en_US |
dc.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic | en_US |
dc.relation.ispartof | Inorganic Chemistry | en_US |
dc.title | Electronic spectra and photophysics of platinum(II) complexes with α-diimine ligands. Mixed complexes with halide ligands | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ic00063a052 | - |
dc.identifier.scopus | eid_2-s2.0-33751385732 | en_US |
dc.identifier.volume | 32 | en_US |
dc.identifier.issue | 11 | en_US |
dc.identifier.spage | 2518 | en_US |
dc.identifier.epage | 2524 | en_US |
dc.identifier.isi | WOS:A1993LE48900052 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Miskowski, VM=6603008214 | en_US |
dc.identifier.scopusauthorid | Houlding, VH=6602351870 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Wang, Y=36072665800 | en_US |
dc.identifier.issnl | 0020-1669 | - |