Photophysical Properties of Self-Assembled Multinuclear Platinum Metallacycles with Different Conformational Geometries

	Photophysical Properties of Self-Assembled Multinuclear Platinum Metallacycles with Different Conformational Geometries
	Chen, Jun-Sheng 1,2; Zhao, Guang-Jiu 1; Cook, Timothy R.3; Han, Ke-Li 1; Stang, Peter J.3
刊名	journal of the american chemical society
	2013-05-01
卷号	135 期号:17 页码:6694-6702
ISSN号	0002-7863
通讯作者	韩克利 ; peter j. stang
产权排序	待补充
合作状况	英
英文摘要	in this work, spectroscopic techniques and quantum chemistry calculations were used to investigate the photophysical properties of various multinuclear platinum complexes with different conformational geometries. this suite of complexes includes a pt-pyridyl square, a pt-carboxylate triangle, and a mixed pt-pyridyl-carboxylate rectangle, as well as two mononuclear pt model complexes. studying the individual molecular precursors in the context of larger assemblies is important to provide a complete understanding of the factors governing the observed photophysical properties of a given system. the absorption and emission bands of the parent linear dipyridyl donor (ligand 1) are largely preserved in the [4 + 4] square and the multicomponent [4 + 2 + 2] rectangle (3 and 4, respectively), with significant red shifts. the [3 + 3] pt-carboxylate triangle containing p-phthalic acid is nonemissive. phosphorescence and nanosecond transient spectroscopy on 3 and 4 reveal that the introduction of platinum atoms enhances spin-orbital coupling, thereby increasing the rate of intersystem crossing. this phenomenon is consistent with the low fluorescence quantum yields and short fluorescence lifetimes of 3 and 4. moreover, the electronic structures for the ground state and low-lying excited states of these compounds were studied using quantum chemistry calculations. the fluorescent states of the platinum complexes are local excited states of ligand-centered pi-pi* transition features, whereas the nonfluorescent states are intramolecular charge-transfer states. these low-lying intramolecular charge-transfer states are responsible for the nonemissive nature of small molecules 1 and 2 and triangle s. as the interactions between these components determine the properties of their corresponding assemblies, we establish novel excited-state decay mechanisms which dictate the observed spectra.
学科主题	物理化学
WOS标题词	science & technology ; physical sciences
类目[WOS]	chemistry, multidisciplinary
研究领域[WOS]	chemistry
关键词[WOS]	density-functional calculations ; triplet excited-states ; gaussian-basis sets ; charge-transfer ; molecular design ; atoms li ; complexes ; coordination ; fluorescence ; symmetry
收录类别	SCI
资助信息	1，1
原文出处	6702
语种	英语
WOS记录号	WOS:000318469100046
公开日期	2014-09-11
内容类型	期刊论文
源URL	[http://159.226.238.44/handle/321008/119411]
专题	大连化学物理研究所_中国科学院大连化学物理研究所
作者单位	1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 3.Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA
推荐引用方式 GB/T 7714	Chen, Jun-Sheng,Zhao, Guang-Jiu,Cook, Timothy R.,et al. Photophysical Properties of Self-Assembled Multinuclear Platinum Metallacycles with Different Conformational Geometries[J]. journal of the american chemical society,2013,135(17):6694-6702.
APA	Chen, Jun-Sheng,Zhao, Guang-Jiu,Cook, Timothy R.,Han, Ke-Li,&Stang, Peter J..(2013).Photophysical Properties of Self-Assembled Multinuclear Platinum Metallacycles with Different Conformational Geometries.journal of the american chemical society,135(17),6694-6702.
MLA	Chen, Jun-Sheng,et al."Photophysical Properties of Self-Assembled Multinuclear Platinum Metallacycles with Different Conformational Geometries".journal of the american chemical society 135.17(2013):6694-6702.