Bioinspired Orientation of beta-Substituents on Porphyrin Antenna   Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity

doi:10.1021/acs.inorgchem.6b02481

CORC > 北京大学 > 化学与分子工程学院

	Bioinspired Orientation of beta-Substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity
	Ning, Yingying ; Ke, Xian-Sheng ; Hu, Ji-Yun ; Liu, Yi-Wei ; Ma, Fang ; Sun, Hao-Ling ; Zhang, Jun-Long
刊名	INORGANIC CHEMISTRY
	2017
关键词	LANTHANIDE(III) MONOPORPHYRINATE COMPLEXES ENERGY-TRANSFER UP-CONVERSION MESO-TETRAARYLPORPHYRINS SENSITIZED LUMINESCENCE ELECTRONIC EXCITATION TEMPERATURE SENSORS QUANTUM YIELDS METAL EUROPIUM
DOI	10.1021/acs.inorgchem.6b02481
英文摘要	"Configurational isomerism" is an important approach found in naturally occurring chlorophylls to modulate light harvesting function without significant structural changes; however, this feature has been seldom applied in design of antenna ligands for lanthanide (Ln) sensitization. In this work, we introduced a bioinspired approach by orientation of beta-dilactone moieties on porphyrinates, namely cis-/trans-porphodilactones, to modulate the energy transfer process from the lowest triplet excited state of the ligand (T-1) to the emitting level of ytterbium(III) (F-2(5/2), Yb). Interestingly, near-infrared (NIR) emission of Yb(III) could be switched "on" by the cis-porphodilactone ligand, while the trans-isomer renders Yb(III) emission "off' and the ratio of quantum yields is similar to 8. Analysis of the structure-photophysical properties relationship suggests that the significant emission difference is correlated to the energy gaps between T-1 and Yb (1152 cm(-1) in the cis- vs-25 cm(-1) in the trans isomer). More interestingly, due to back energy transfer (BEnT), the Yb(III) complex of cis-porphodilactone exhibits NIR emission with high thermosensitivity (4.0% C-1 in solution and 4.9% C-1 in solid state), comparable to previously reported terbium (Tb) and europium (Eu) visible emitters, in contrast to the trivial emission changes of the trans-isomer and porphyrin and porpholactone analogues. This work opens up new access to design NIR emissive Ln complexes by bioinspired modification of antenna ligands.; National Key Basic Research Support Foundation of China (NKBRSFC) [2015CB856301]; NSFC [21571007, 21271013, 21321001]; SCI(E); ARTICLE; 4; 1897-1905; 56
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/475088]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Ning, Yingying,Ke, Xian-Sheng,Hu, Ji-Yun,et al. Bioinspired Orientation of beta-Substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity[J]. INORGANIC CHEMISTRY,2017.
APA	Ning, Yingying.,Ke, Xian-Sheng.,Hu, Ji-Yun.,Liu, Yi-Wei.,Ma, Fang.,...&Zhang, Jun-Long.(2017).Bioinspired Orientation of beta-Substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity.INORGANIC CHEMISTRY.
MLA	Ning, Yingying,et al."Bioinspired Orientation of beta-Substituents on Porphyrin Antenna Ligands Switches Ytterbium(III) NIR Emission with Thermosensitivity".INORGANIC CHEMISTRY (2017).