para-Quinodimethane-bridged perylene dimers and pericondensed quaterrylenes: the effect of the fusion mode on the ground states and physical properties.

Citation data:

Chemistry (Weinheim an der Bergstrasse, Germany), ISSN: 1521-3765, Vol: 20, Issue: 36, Page: 11410-20

Publication Year:
2014
Usage 24
Abstract Views 24
Captures 29
Readers 29
Citations 33
Citation Indexes 33
Repository URL:
http://hdl.handle.net/10754/563659
PMID:
25056662
DOI:
10.1002/chem.201402831
Author(s):
Das, Soumyajit; Lee, Sangsu; Son, Minjung; Zhu, Xiaojian; Zhang, Wenhua; Zheng, Bin; Hu, Pan; Zeng, Zebing; Sun, Zhe; Zeng, Wangdong; Li, Run-Wei; Huang, Kuo-Wei; Ding, Jun; Kim, Dongho; Wu, Jishan Show More Hide
Publisher(s):
Wiley-Blackwell; Wiley-VCH Verlag
Tags:
Chemistry; aromaticity; polycycles; radicals; rylene; zethrene
article description
Polycyclic hydrocarbon compounds with a singlet biradical ground state show unique physical properties and promising material applications; therefore, it is important to understand the fundamental structure/biradical character/physical properties relationships. In this study, para-quinodimethane (p-QDM)-bridged quinoidal perylene dimers 4 and 5 with different fusion modes and their corresponding aromatic counterparts, the pericondensed quaterrylenes 6 and 7, were synthesized. Their ground-state electronic structures and physical properties were studied by using various experiments assisted with DFT calculations. The proaromatic p-QDM-bridged perylene monoimide dimer 4 has a singlet biradical ground state with a small singlet/triplet energy gap (-2.97 kcal mol(-1)), whereas the antiaromatic s-indacene-bridged N-annulated perylene dimer 5 exists as a closed-shell quinoid with an obvious intramolecular charge-transfer character. Both of these dimers showed shorter singlet excited-state lifetimes, larger two-photon-absorption cross sections, and smaller energy gaps than the corresponding aromatic quaterrylene derivatives 6 and 7, respectively. Our studies revealed how the fusion mode and aromaticity affect the ground state and, consequently, the photophysical properties and electronic properties of a series of extended polycyclic hydrocarbon compounds.