Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited   States: A Bioinspired Approach to Design Phosphorescent   Metalloporphyrinoids

doi:10.1021/jacs.5b06332

CORC > 北京大学 > 化学与分子工程学院

	Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids
	Ke, Xian-Sheng ; Zhao, Hongmei ; Zou, Xiaoran ; Ning, Yingying ; Cheng, Xin ; Su, Hongmei ; Zhang, Jun-Long
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2015
关键词	LIGHT-EMITTING-DIODES SYNTHETIC ANALOGS QUANTUM YIELDS UP-CONVERSION PHOTOPHYSICAL PROPERTIES EXPANDED PORPHYRINS CHLOROPHYLLS SPECTROSCOPY SPECTRA PHOTOPROTECTION
DOI	10.1021/jacs.5b06332
英文摘要	Learning nature's approach to modulate photophysical properties of NIR porphyrinoids by fine-tuning beta-substituents including the number and position, in a manner similar to naturally occurring chlorophylls, has the potential to circumvent the disadvantages of traditional "extended pi-conjugation" strategy such as stability, molecular size, solubility, and undesirable pi-pi stacking. Here we show that such subtle structural changes in Pt(II) or Pd(II) cis/trans-porphodilactones (termed by cis/trans-Pt/Pd) influence photophysical properties of the lowest triplet excited states including phosphorescence, Stokes shifts, and even photosensitization ability in triplet triplet annihilation reactions with rubrene. Prominently, the overall upconversion capability (eta, eta = epsilon.Phi(UC)) of Pd or Pt trans-complex is 10(4) times higher than that of cis-analogue. Nanosecond time-resolved infrared (TR-IR) spectroscopy experiments showed larger frequency shift of nu(C=O) bands (ca. 10 cm(-1)) of cis-complexes than those of trans-complexes in the triplet excited states. These spectral features, combining with TD-DFT calculations, suggest the strong electronic coupling between the lactone moieties and the main porphyrin chromophores and thus the importance of precisely positioning beta-substituents by mimicking chlorophylls, as an alternative to "extended pi-conjugation", in designing NIR active porphyrinoids.; National Key Basic Research Support Foundation of China (NKBRSFC) [2010CB912302, 2015CB856300]; NSFC [20971007, 21271013, 21321001, 21333012, 21425313]; CAS project [XDB12020200]; SCI(E); EI; PubMed; ARTICLE; hongmei@iccas.ac.cn; zhangjunlong@pku.edu.cn; 33; 10745-10752; 137
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/417082]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Ke, Xian-Sheng,Zhao, Hongmei,Zou, Xiaoran,et al. Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015.
APA	Ke, Xian-Sheng.,Zhao, Hongmei.,Zou, Xiaoran.,Ning, Yingying.,Cheng, Xin.,...&Zhang, Jun-Long.(2015).Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
MLA	Ke, Xian-Sheng,et al."Fine-Tuning of beta-Substitution to Modulate the Lowest Triplet Excited States: A Bioinspired Approach to Design Phosphorescent Metalloporphyrinoids".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015).