Luminescent platinum complexes: tuning and using the excited state

Paw, Witold; Cummings, Scott D.; Mansour, Michael; Connick, Williams B.; Geiger, David K.; Eisenberg, Richard

doi:10.1016/s0010-8545(98)90023-6

Cited by 280 publications

(172 citation statements)

References 51 publications

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“…[5,6] The CT absorption bands are negatively solvatochromic (CH 2 Cl 2 / CH 3 CN; H-1: 733/672 nm; H-2: 745/683 nm; Me-1: 740/ 672 nm). The dinuclear complex H-3 displays two such catecholato!diimine LLCT bands, with the high-energy band being positively solvatochromic and the low-energy band being negatively solvatochromic (CH 2 Cl 2 /CH 3 CN; 640/ 672 nm and 885/876 nm).…”

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confidence: 99%

“…In analogy to known catecholatoplatinum(II) complexes [5][6][7]12] the neutral complexes H-1, H-2, H-3 and Me-1 are non-luminescent at room temperature in fluid solution. Remarkably, the anionic complexes 1 À , 2 À and 3 À do emit at 512/528 nm, 503/518 nm and 514/533 nm (CH 2 Cl 2 / CH 3 CN), respectively, when excited at a wavelength of 419 nm.…”

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confidence: 99%

“…[13] In frozen solution (77 K) the complex [Pt(dbbpy)(O 2 phen)Pt(dbcat)] displays a weak low-energy 3 LLCT emission band at 700 nm. [6] [14,15] However, the deprotonated ligand itself and the anionic dichloro complex 4 À are non-emissive under these conditions. Thus the particular geometric and electronic structure of 1 À , 2 À and 3 À should be responsible for the observed room-temperature luminescence.…”

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confidence: 99%

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Platinum(II) Complexes with Non‐Innocent Ligands: Solid‐Phase Synthesis, Redox Chemistry and Luminescence

Heinze

Reinhardt

2008

Chemistry A European J

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Platinum(II) Complexes with Non‐Innocent Ligands: Solid‐Phase Synthesis, Redox Chemistry and Luminescence

Heinze

Reinhardt

2008

Chemistry A European J

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“…[20] This result further encouraged us to employ dithiolato-bipyridine platinum(II) complexes. [21] The ligand-field splitting of these complexes is large enough to avoid quenching low-lying LF excited states, because of the strong s-donor ability of the dithiolato ligand, p-acceptor ability of the bipyridine ligand, and the 5d platinum(II) ion. This fact is well reflected in a peculiar low-lying (500-700 nm) interligand CT transition from the dithiolene(p) to bipyridine(p*) unit, which results in a longlived triplet excited state and phosphorescence from this state at ambient temperature in solution.…”

Section: Introductionmentioning

confidence: 99%

“…This fact is well reflected in a peculiar low-lying (500-700 nm) interligand CT transition from the dithiolene(p) to bipyridine(p*) unit, which results in a longlived triplet excited state and phosphorescence from this state at ambient temperature in solution. [21] These characteristic electronic structures and absorptions of dithiolato-bipyridine platinum(II) complexes should provide azobenzene with high efficiency for photoisomerization and further extension of the photoresponse at longer wavelengths.…”

Section: Introductionmentioning

confidence: 99%

trans–cis Photoisomerization of Azobenzene‐Conjugated Dithiolato‐Bipyridine Platinum(II) Complexes: Extension of Photoresponse to Longer Wavelengths and Photocontrollable Tristability

Sakamoto

Kume

Sugimoto

et al. 2009

Chemistry A European J

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Azobenzene derivatives modified with dithiolato-bipyridine platinum(II) complexes were synthesized, revealing their highly extended photoresponses to the long wavelength region as well as unique photocontrollable tristability. The absorptions of trans-1 and trans-2 with one azobenzene group on the dithiolene and bipyridine ligands, respectively, cover the range from 300 to 700 nm. These absorptions are ascribed, by means of time-dependent (TD)DFT calculations, to transitions from dithiolene(pi) to bipyridine(pi*), namely, interligand charge transfer (CT), pi-pi*, and n-pi* transitions of the azobenzene unit, and pi-pi* transitions of the bipyridine ligand. In addition, only trans-1 shows distinctive electronic bands, assignable to transitions from the dithiolene(pi) to azobenzene(pi*), defined as intraligand CT. Complex 1 shows photoisomerization behavior opposite to that of azobenzene: trans-to-cis and cis-to-trans conversions proceed with 405 and 312 nm irradiation, which correspond to excitation with the intraligand CT, and pi-pi* bands of the azobenzene and bipyridine units, respectively. In contrast, complex 2 shows photoisomerization similar to that of azobenzene: trans-to-cis and cis-to-trans transformations occur with 365 and 405 nm irradiation, respectively. Irradiation at 578 nm, corresponding to excitation of the interligand CT transitions, results in cis-to-trans conversion of both 1 and 2, which is the longest wavelength ever reported to effect the photoisomerization of the azobenzene group. The absorption and photochromism of 4, which has azobenzene groups on both the dithiolato and bipyridine ligands, have characteristics quite similar to those of 1 and 2, which furnishes 4 with photocontrollable tristability in a single molecule using light at 365, 405, and 578 nm. We also clarified that 1 and 2 have high photoisomerization efficiencies, and good thermal stability of the cis forms. Complexes 3 and 5 have almost the identical photoresponse to those of their positional isomers, complexes 2 and 4.

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Luminescent Star-Shaped Zinc(II) and Platinum(II) Complexes Based on Star-Shaped 2,2′-Dipyridylamino-Derived Ligands

Seward

Pang

Wang

2002

Eur. J. Inorg. Chem.

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New ZnII and PtII complexes of the star‐shaped ligands 2,4,6‐tris(2,2′‐dipyridylamino)‐1,3,5‐triazine (tdat), 1,3,5‐tris(2,2′‐dipyridylamino)benzene (tdab), 2,4,6‐tris[p‐(2,2′‐dipyridylamino)phenyl]‐1,3,5‐triazine (tdapt) and 1,3,5‐tris[p‐(2,2′‐dipyridylamino)phenyl]benzene (tdapb) have been synthesized and characterized. 1:1, 1:2 and 1:3 (ligand vs. the number of Zn atoms) ZnII complexes of the tdat ligand have been identified. The 1:1 and 1:2 ZnII complexes of tdat are dynamic in solution. For the tdab, tdapt and tdapb ligands, only 1:3 complexes of PtII and ZnII have been isolated. Single‐crystal X‐ray diffraction analyses have been carried out for some of these new complexes, which revealed that there is a distinct difference in the arrangement of star‐shaped ligands in the complexes of ZnII and those of PtII. The PtII complexes of tdat and tdab adopt an unusual “bowl” shape and stack in a “head‐to‐tail” fashion in the crystal lattice. In contrast, the corresponding ZnII complexes do not have a “bowl” shape. The difference between the ZnII complexes and the PtII complexes can be attributed to the different coordination geometry preferred by the two metal ions. The ZnII complex of tdapb displays several crystal motifs, two of which contain benzene molecules in the crystal lattices. All complexes are luminescent in the blue region, attributable to ligand‐based π ⇄ π* transitions. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Luminescent platinum complexes: tuning and using the excited state

Cited by 280 publications

References 51 publications

Platinum(II) Complexes with Non‐Innocent Ligands: Solid‐Phase Synthesis, Redox Chemistry and Luminescence

Platinum(II) Complexes with Non‐Innocent Ligands: Solid‐Phase Synthesis, Redox Chemistry and Luminescence

trans–cis Photoisomerization of Azobenzene‐Conjugated Dithiolato‐Bipyridine Platinum(II) Complexes: Extension of Photoresponse to Longer Wavelengths and Photocontrollable Tristability

Luminescent Star-Shaped Zinc(II) and Platinum(II) Complexes Based on Star-Shaped 2,2′-Dipyridylamino-Derived Ligands

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