TY - JOUR
T1 - Facile Preparation of Highly Luminescent Materials by Electrostatic Immobilization of Anionic Metal Complex onto Anion-Exchanger as Exemplified with Tri-Terbium(III) Cluster Complex of Thiacalix[4]arene-p-tetrasulfonate
AU - Shiraishi, Narumi
AU - Karashimada, Ryunosuke
AU - Iki, Nobuhiko
PY - 2019/1/1
Y1 - 2019/1/1
N2 - We propose a strategy to prepare luminescence materials via simple and organic solvent-free fashion by mixing an anionic luminescent complex with an anion exchanging support. As a proof-of-concept, we employed the heptaanionic TbIII complex Tb3TCAS2 (TCAS = thiacalix[4]arene-p-tetrasulfonate) and QAE Sephadex A-25, a dextran support bearing anion exchanging groups. By stirring a mixture of TCAS and dextran (1.0 ¯mol Tb3TCAS2/50 mg dextran), 99.8% of Tb3TCAS2 was successfully immobilized within 2 h. The electrostatic interactions were strong enough to irreversibly bind Tb3TCAS2 to the dextran. The material exhibited TbIII-centered luminescence upon excitation of the TCAS center. The luminescent lifetime and quantum yield were 1.18 ms and 45.5%, respectively. When the amount of Tb3TCAS2 immobilized on the dextran was reduced to 1.0 nmol/50 mg dextran, the lifetime increased to 1.32 ms, suggesting concentration quenching above 1.0 ¯mol Tb3TCAS2/50 mg dextran. On the other hand, the luminescence quantum yield decreased to 3.1%, suggesting that the absorption of excited light by the support was not negligible. Preparation of the materials in D2O resulted in increases in the lifetime and quantum yields to 1.32 ms and 44%, respectively.
AB - We propose a strategy to prepare luminescence materials via simple and organic solvent-free fashion by mixing an anionic luminescent complex with an anion exchanging support. As a proof-of-concept, we employed the heptaanionic TbIII complex Tb3TCAS2 (TCAS = thiacalix[4]arene-p-tetrasulfonate) and QAE Sephadex A-25, a dextran support bearing anion exchanging groups. By stirring a mixture of TCAS and dextran (1.0 ¯mol Tb3TCAS2/50 mg dextran), 99.8% of Tb3TCAS2 was successfully immobilized within 2 h. The electrostatic interactions were strong enough to irreversibly bind Tb3TCAS2 to the dextran. The material exhibited TbIII-centered luminescence upon excitation of the TCAS center. The luminescent lifetime and quantum yield were 1.18 ms and 45.5%, respectively. When the amount of Tb3TCAS2 immobilized on the dextran was reduced to 1.0 nmol/50 mg dextran, the lifetime increased to 1.32 ms, suggesting concentration quenching above 1.0 ¯mol Tb3TCAS2/50 mg dextran. On the other hand, the luminescence quantum yield decreased to 3.1%, suggesting that the absorption of excited light by the support was not negligible. Preparation of the materials in D2O resulted in increases in the lifetime and quantum yields to 1.32 ms and 44%, respectively.
KW - Luminescent materials
KW - Terbium
KW - Thiacalixarene
UR - http://www.scopus.com/inward/record.url?scp=85074478892&partnerID=8YFLogxK
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U2 - 10.1246/bcsj.20190190
DO - 10.1246/bcsj.20190190
M3 - Article
AN - SCOPUS:85074478892
VL - 92
SP - 1847
EP - 1852
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 11
ER -