Tuning Photophysics and Nonlinear Absorption of Bipyridyl Platinum(II) Bisstilbenylacetylide Complexes by Auxiliary Substituents

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• 作者：Zhongjing Li ; Ekaterina Badaeva ; Dapeng Zhou ; Josiah Bjorgaard ; Ksenija D. Glusac ; Svetlana Killina ; Wenfang Sun
• 刊名：The Journal of Physical Chemistry A
• 出版年：2012
• 出版时间：May 24, 2012
• 年：2012
• 卷：116
• 期：20
• 页码：4878-4889
• 全文大小：673K
• 年卷期：v.116,no.20(May 24, 2012)
• ISSN：1520-5215

文摘

The photophysics of six bipyridyl platinum(II) bisstilbenylacetylide complexes with different auxiliary substituents are reported. These photophysical properties have been investigated in detail by UV鈥搗is, photoluminescence (both at room temperature and at 77 K) and transient absorption (nanosecond and femtosecond) spectroscopies, as well as by linear response time-dependent density functional theory (TD-DFT) calculations. The photophysics of the complexes are found to be dominated by the singlet and triplet 蟺,蟺* transitions localized at the stilbenylacetylide ligands with strong admixture of the metal-to-ligand (MLCT) and ligand-to-ligand (LLCT) charge-transfer characters. The interplay between the 蟺,蟺* and MLCT/LLCT states depends on the electron-withdrawing or -donating properties of the substituents on the stilbenylacetylide ligands. All complexes exhibit remarkable reverse saturable absorption (RSA) at 532 nm for nanosecond laser pulses, with the complex that contains the NPh₂ substituent giving the strongest RSA and the complex with NO₂ substituent showing the weakest RSA.