有机分子荧光课件.pptVIP

XMUGXQPFS03-01ChapterThreXMUGXQPFS03-01FluorophoresOrganicmoleculefluorescencemetal–ligandcompoundXMUGXQPFS03-013.1有机分子荧光l有机分子的电子结构一般情况下，n-?*跃迁所需能量小。但当n电子与溶剂作用，如形成氢键、质子化等，使n轨道能量降低，n-?*跃迁能量增大XMUGXQPFS03-01l分子激发态的多样XMUGXQPFS03-01l电子激发态的类型——单线态与三线态ISC效率的高低决定于自旋-轨道耦合程度。增加重原子常常促进ISC过程XMUGXQPFS03-013.1.1有机分子荧光与结构的关XMUGXQPFS03-01l电子离域程度对荧光的影XMUGXQPFS03-01例21,2–二苯乙XMUGXQPFS03-01l刚性平面结构例1荧光素与酚酞XMUGXQPFS03-01例2笏与联苯??1??0.2FF例3偶氮苯与杂氮XMUGXQPFS03-01例4金属配合XMUGXQPFS03-01例5荧光衍生XMUGXQPFS03-01例6联萘与XMUGXQPFS03-01l取代基的影XMUGXQPFS03-01吸收增强如何理解XMUGXQPFS03-01酚盐吸收性XMUGXQPFS03-0120040300

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XMUGXQPFS03-01重原子效XMUGXQPFS03-01重原子效XMUGXQPFS03-01l最低单重态的性XMUGXQPFS03-01含氮杂环有机XMUGXQPFS03-01含羰基有机物0.991.001.010.840.930.870.8720040300

XMUGXQPFS03-01l抗磁XMUGXQPFS03-01抗磁XMUGXQPFS03-01抗磁性N.V.BloughandD.J.Simpson,“Chemicalmediatedfluorescneceyieldswitchinginnitroxide-fluorophoreadducts:opticalsensorsofradical/redoxreactions”,J.Am.Chem.Soc,1988,110,1915-191720040300

XMUGXQPFS03-01抗磁性Reference0.01220040300

XMUGXQPFS03-01ReferenceKazuyukeIshii,NagaoKobayashi,“Theexcitedmultipletstatesofmetalloporphyrinsandmetallophthalocyaninescoordinatedoflinkedtonitroxideradicals”CoordinationChemistryReviews,198(2000),231-25020040300

XMUGXQPFS03-013.2Metal–ligandcompoundsMLCTLMCTⅡⅢⅣXMUGXQPFS03-013.2Metal–ligandcompoundXMUGXQPFS03-01配体发XMUGXQPFS03-01MLCTMetal–ligandchargetransfeXMUGXQPFS03-0120040300

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XMUGXQPFS03-01引自“荧光分析法”陈国珍等人编写。问题：Demas等人认为?-二亚胺类配体易被还原，与铂系元素形成的配合物应为MLCTXMUGXQPFS03-013.2.1铂系金属有机配体化合物代表性工XMUGXQPFS03-01Re