期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 118, 期 30, 页码 5608-5613出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp503318u
关键词
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资金
- FAPESP (Fundacao de Amparo Pesquisa do estado de Sao Paulo) [2011/06489-6, 2011/12399-0]
- CNPq (Conselho Nacional de Desenvolvimento Cientifico e Tecnologico)
- Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)
- Air Force Office of Scientific Research [FA9550-12-1-0028]
Herein, we report on the two-absorption cross-section spectrum of trans-Pt(PBu3)(2) (C equivalent to C-C6H4-C equivalent to C-C6H5)(2) (PE2) platinum acetylide complex employing the femtosecond wavelength-tunable Z-scan technique. The PE2 complex can be visualized as two branches containing two phenylacetylene units, each one linked by a platinum center, completely transparent in the visible region. Because of this structure, large delocalization of pi-electrons allied to the strong intramolecular interaction between the branches is expected. The 2PA absorption spectrum was measured using the femtosecond wavelength-tunable Z-scan technique with low repetition rate (1 kHz), in order to obtain the 2PA spectrum without excited-state contributions. Our results reveal that PE2 in dichloromethane solution presents two 2PA allowed bands located at 570 and 710 nm, with cross section of about 320 and 45 GM, respectively. The first one is related to the strong intramolecular interaction between the molecule's branches due to the presence of platinum atom, while the second one is associated with the breaking of symmetry of the chromophore in solution due, most probably to a large twisting angle of the ligand's phenyl rings relative to the Pt core.
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