title: Energy transfer and spectroscopic characterization of a perylenetetracarboxylic diimide (PDI) hexamer.
abstract: We report a comprehensive study on a newly synthesized perylenetetracarboxylic diimide (PDI) hexamer together with its corresponding monomer and dimer by means of steady-state absorption and fluorescence as well as femtosecond broadband transient absorption measurements. The structure of the PDI hexamer is nearly arranged in a 3-fold symmetry by three identical and separated dimers. This unique structure makes the excited state energy relaxation processes more complex due to the existence of two different intramolecular interactions: a strong interaction between face-to-face PDIs in dimers and a relatively weak interaction between the three separated PDI dimers. The steady-state spectra and the ground state structural optimization show that the steric effect plays a dominant role in keeping the formation of the face-to-face stacked PDI-dimer within the PDI-hexamer, indicating that some level of a pre-associated excimer had formed already in the ground state for the dimer in the hexamer. Femtosecond transient absorption experiments on the PDI hexamer reveal a fast (∼200 fs) localization process and a sequential relaxation to a pre-associated excimer trap state from the delocalized exciton state with about 1.2 ps after the initially delocalized excitation. Meanwhile, excitation energy transfer among the three separated dimers within the PDI-hexamer is also revealed by the anisotropic femtosecond pump-probe transient experiments, where the hopping time is about 2.8 ps. A relaxed excimer state is further formed in 7.9 ps after energy hopping and conformational relaxation.
authors.affiliation: Beijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China. andong@iccas.ac.cn guoqj@iccas.ac.cn.
authors.forename: Saran
authors.initials: S
authors.lastname: Long
authors.forename: Yingying
authors.initials: Y
authors.lastname: Wang
authors.forename: Silvije
authors.initials: S
authors.lastname: Vdović
authors.forename: Meng
authors.initials: M
authors.lastname: Zhou
authors.forename: Linyin
authors.initials: L
authors.lastname: Yan
authors.forename: Yingli
authors.initials: Y
authors.lastname: Niu
authors.forename: Qianjin
authors.initials: Q
authors.lastname: Guo
authors.forename: Andong
authors.initials: A
authors.lastname: Xia
mesh_terms: D019281:Dimerization; D004735:Energy Transfer; D007094:Imides / Q000737:chemistry*; D010569:Perylene / Q000031:analogs & derivatives* / Q000737:chemistry; D011789:Quantum Theory; D013050:Spectrometry, Fluorescence
chemical_list: D007094:Imides; C517085:perylenetetracarboxylic diimide; D010569:Perylene