Coordination Nanosheets Based on Terpyridine-Zinc(II) Complexes: As Photoactive Host Materials.
Photoluminescent coordination nanosheets (CONASHs) comprising three-way terpyridine (tpy) ligands and zinc(II) ions are created by allowing the two constitutive components to react with each other at a liquid/liquid interface. Taking advantage of bottom-up CONASHs, or flexibility in organic ligand design and coordination modes, we demonstrate the diversity of the tpy-zinc(II) CONASH in structures and photofunctions. A combination of 1,3,5-tris[4-(4'-2,2':6',2″-terpyridyl)phenyl]benzene (1) and Zn(BF4)2affords a cationic CONASH featuring the bis(tpy)Zn complex motif (1-Zn), while substitution of the zinc source with ZnSO4realizes a charge-neutral CONASH with the [Zn2(μ-O2SO2)2(tpy)2] motif [1-Zn2(SO4)2]. The difference stems from the use of noncoordinating (BF4-) or coordinating and bridging (SO42-) anions. The change in the coordination mode alters the luminescence (480 nm blue in 1-Zn; 552 nm yellow in 1-Zn2(SO4)2). The photophysical property also differs in that 1-Zn2(SO4)2shows solvatoluminochromism, whereas 1-Zn does not. Photoluminescence is also modulated by the tpy ligand structure. 2-Zn contains triarylamine-centered terpyridine ligand 2 and features the bis(tpy)Zn motif; its emission is substantially red-shifted (590 nm orange) compared with that of 1-Zn. CONASHs 1-Zn and 2-Zn possess cationic nanosheet frameworks with counteranions (BF4-), and thereby feature anion exchange capacities. Indeed, anionic xanthene dyes were taken up by these nanosheets, which undergo quasi-quantitative exciton migration from the host CONASH. This series of studies shows tpy-zinc(II) CONASHs as promising potential photofunctional nanomaterials.
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|Japan Society for the Promotion of Science (JSPS) , Ichibancho, Chiyoda-ku, Tokyo 102-8471, Japan.
Takamasa
T
Tsukamoto
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Kenji
K
Takada
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.|JST-PRESTO , 4-1-8 Honjcho, Kawaguchi, Saitama 332-0012, Japan.
Ryota
0000-0002-8702-1378
R
Sakamoto
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Ryota
R
Matsuoka
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Ryojun
R
Toyoda
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Hiroaki
H
Maeda
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Toshiki
T
Yagi
Department of Materials and Life Science, Seikei University , 3-3-1 Kichijoji-kitamachi, Musashino-shi, Tokyo 180-8633, Japan.
Michihiro
M
Nishikawa
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Naoaki
N
Shinjo
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Shuntaro
S
Amano
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Tadashi
T
Iokawa
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Narutaka
N
Ishibashi
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Tsugumi
T
Oi
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Koshiro
K
Kanayama
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Rina
R
Kinugawa
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Yoichiro
Y
Koda
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Toshiyuki
T
Komura
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Shuhei
S
Nakajima
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Ryota
R
Fukuyama
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Nobuyuki
N
Fuse
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Makoto
M
Mizui
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Masashi
M
Miyasaki
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Yutaro
Y
Yamashita
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Kuni
K
Yamada
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Wenxuan
W
Zhang
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Ruocheng
R
Han
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Wenyu
W
Liu
Department of Materials and Life Science, Seikei University , 3-3-1 Kichijoji-kitamachi, Musashino-shi, Tokyo 180-8633, Japan.
Taro
T
Tsubomura
Department of Chemistry, Graduate School of Science, The University of Tokyo , 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Hiroshi
H
Nishihara