TY - JOUR
T1 - Self-Assembly of a Trilanthanide(III) Core Sandwiched between Two Thiacalix[4]arene Ligands
AU - Iki, Nobuhiko
AU - Tanaka, Teppei
AU - Hiro-oka, Shoichi
AU - Shinoda, Kozo
N1 - Funding Information:
This research was supported by the Japan Society for the Promotion of Science (JSPS) through Grants-in-Aid for Scientific Research (KAKENHI) (grant no. 25288061). N. I. wishes to thank Prof. Kazuyuki Tohji from Tohoku University for his helpful guidance to XAFS.
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/11
Y1 - 2016/11
N2 - Thiacalix[4]arene-p-tetrasulfonate (TCAS) incorporated a trilanthanide(III) core to form a 3:2 Ln3TCAS2complex in aqueous solution. The self-assembly process was monitored at pH 9.5 and 7.4 by HPLC for all lanthanides except PmIII. Self-assembly took place in three steps. First, TCAS and LnIIIformed a 1:1 Ln1TCAS1complex. Second, two molecules of Ln1TCAS1condensed to form Ln2TCAS2. Finally, Ln2TCAS2reacted with additional LnIIIto form Ln3TCAS2. This self-assembly exhibited extremely slow kinetics and required 1–4 d to reach completion. Small amounts of minor species, including Ln1TCAS1, Ln2TCAS2, and Ln4TCAS2, were observed depending on the LnIIIspecies and pH. The generation of these species is controlled by factors such as the stability of the Ln-TCAS species, effect of coordinated water, and size of LnIII. XAFS spectra of aqueous Gd3TCAS2solutions established the solution structure of the tri-LnIIIcluster sandwiched by two TCAS ligands.
AB - Thiacalix[4]arene-p-tetrasulfonate (TCAS) incorporated a trilanthanide(III) core to form a 3:2 Ln3TCAS2complex in aqueous solution. The self-assembly process was monitored at pH 9.5 and 7.4 by HPLC for all lanthanides except PmIII. Self-assembly took place in three steps. First, TCAS and LnIIIformed a 1:1 Ln1TCAS1complex. Second, two molecules of Ln1TCAS1condensed to form Ln2TCAS2. Finally, Ln2TCAS2reacted with additional LnIIIto form Ln3TCAS2. This self-assembly exhibited extremely slow kinetics and required 1–4 d to reach completion. Small amounts of minor species, including Ln1TCAS1, Ln2TCAS2, and Ln4TCAS2, were observed depending on the LnIIIspecies and pH. The generation of these species is controlled by factors such as the stability of the Ln-TCAS species, effect of coordinated water, and size of LnIII. XAFS spectra of aqueous Gd3TCAS2solutions established the solution structure of the tri-LnIIIcluster sandwiched by two TCAS ligands.
KW - Calixarenes
KW - Lanthanides
KW - Luminescence
KW - Self-assembly
UR - http://www.scopus.com/inward/record.url?scp=84993978157&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84993978157&partnerID=8YFLogxK
U2 - 10.1002/ejic.201600762
DO - 10.1002/ejic.201600762
M3 - Article
AN - SCOPUS:84993978157
VL - 2016
SP - 5020
EP - 5027
JO - Berichte der deutschen chemischen Gesellschaft
JF - Berichte der deutschen chemischen Gesellschaft
SN - 0365-9496
IS - 31
ER -