TY - JOUR
T1 - Tuning the optical properties of 2-Thienylpyridyl iridium complexes through carboranes and anions
AU - Zhu, Lin
AU - Tang, Xiao
AU - Yu, Qi
AU - Lv, Wen
AU - Yan, Hong
AU - Zhao, Qiang
AU - Huang, Wei
N1 - Publisher Copyright:
©2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/3/16
Y1 - 2015/3/16
N2 - Thienylpyridyl iridium(III) complexes containing an o-, m-, or p-carboranylvinyl-2,2′-bipyridine ligand and various counteranions (denoted o-PF6, m-BF4, m-PF6 m- SbF6, m-ClO4, m- OTf, m-NO3, m-BPh4, m-F, m-Cl, and p-PF6) were synthesized by using C-formyl carboranes as starting materials. The solid-state structures of o-PF6, m- PF6, m-ClO4, and m-BF4 showed that the cations form twisted cavities in which the anions are fixed by multiple hydrogen bonds. Anion-hydrogen interactions were investigated for nine m-carborane-based complexes with different counteranions. All carborane-based iridium(III) complexes show similar phosphorescence yields in solution but significantly different emission in the solid state. Anion-exchange titration and theoretical calculations revealed the relationships between structures and optical properties. The size of the anion and C-H••• X anion-hydrogen bonds strongly influence the phosphorescence quantum yield in the solid state. In particular, the Ccar-H •••X hydrogen bonds between the carboranyl unit and the anion play an important role in solid-state phosphorescence. Complex p -PF6 was successfully applied in phosphorescence-lifetime bioimaging owing to its low toxicity and near-infrared emission.
AB - Thienylpyridyl iridium(III) complexes containing an o-, m-, or p-carboranylvinyl-2,2′-bipyridine ligand and various counteranions (denoted o-PF6, m-BF4, m-PF6 m- SbF6, m-ClO4, m- OTf, m-NO3, m-BPh4, m-F, m-Cl, and p-PF6) were synthesized by using C-formyl carboranes as starting materials. The solid-state structures of o-PF6, m- PF6, m-ClO4, and m-BF4 showed that the cations form twisted cavities in which the anions are fixed by multiple hydrogen bonds. Anion-hydrogen interactions were investigated for nine m-carborane-based complexes with different counteranions. All carborane-based iridium(III) complexes show similar phosphorescence yields in solution but significantly different emission in the solid state. Anion-exchange titration and theoretical calculations revealed the relationships between structures and optical properties. The size of the anion and C-H••• X anion-hydrogen bonds strongly influence the phosphorescence quantum yield in the solid state. In particular, the Ccar-H •••X hydrogen bonds between the carboranyl unit and the anion play an important role in solid-state phosphorescence. Complex p -PF6 was successfully applied in phosphorescence-lifetime bioimaging owing to its low toxicity and near-infrared emission.
KW - Carboranes
KW - Chelates
KW - Imaging agents
KW - Iridium
KW - Phosphorescence
UR - http://www.scopus.com/inward/record.url?scp=84924022873&partnerID=8YFLogxK
U2 - 10.1002/chem.201405897
DO - 10.1002/chem.201405897
M3 - 文章
AN - SCOPUS:84924022873
SN - 0947-6539
VL - 21
SP - 4721
EP - 4730
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 12
ER -