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单核和双核金(I)香豆素配合物:发光研究与单线态氧的产生

Mono- and Dinuclear Gold(I) Coumarin Complexes: Luminescence Studies and Singlet Oxygen Production.

作者信息

Sobrerroca Carlota, Angurell Inmaculada, de Aquino Araceli, Romo Guillermo, Jubert Camille, Rodríguez Laura

机构信息

Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica, Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.

Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, 08028, Barcelona, Spain.

出版信息

Chempluschem. 2023 Mar;88(3):e202300020. doi: 10.1002/cplu.202300020.

Abstract

The 4-(thiolmethyl)-7-(diethylamino)-2H-chromen-2-one ligand has been synthesized and used as chromophore in several mono- and dinuclear gold(I) compounds that contain a phosphane at the second coordination position. Four final products were able to obtain in pure form containing one coumarin and one phosphane ligand in the case of PTA (1,3,5-triaza-7-phosphatricyclo[3.3.1.13.7]decane) and PPh (triphenylphosphine); one coumarin and two gold(I)-phosphane groups in the case of phosphane=DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) and two coumarin and two gold(I) atoms in the case of phosphane=DPEphos (bis[(2-diphenylphosphino)phenyl]ether), when it was used a diphosphane. Other diphosphane ligands used were not able to give the desired products in pure form. The luminescent properties of the compounds are governed by the fluorescence of the coumarin moiety in all compounds both for measurements carried out in solution and also immobilized in PMMA organic matrix. Phosphorescence emission can be detected in all cases at 77 K both for the uncoordinated coumarin ligand and the gold(I) derivatives, being more favoured in the presence of the gold(I) heavy atom. The compounds have been used as photosensitizers to generate O with moderate quantum yields values.

摘要

已合成了4-(硫代甲基)-7-(二乙氨基)-2H-色烯-2-酮配体,并将其用作几种单核和双核金(I)化合物中的发色团,这些化合物在第二配位位置含有膦。在使用PTA(1,3,5-三氮杂-7-磷杂三环[3.3.1.13.7]癸烷)和PPh(三苯基膦)的情况下,能够以纯形式获得四种最终产物,其中包含一个香豆素和一个膦配体;在膦=DAPTA(3,7-二乙酰基-1,3,7-三氮杂-5-磷杂双环[3.3.1]壬烷)的情况下,包含一个香豆素和两个金(I)-膦基团,在膦=DPEphos(双[(2-二苯基膦基)苯基]醚)的情况下,包含两个香豆素和两个金(I)原子,此时使用的是双膦。使用的其他双膦配体无法以纯形式得到所需产物。对于在溶液中以及固定在PMMA有机基质中进行的测量,所有化合物中香豆素部分的荧光决定了这些化合物的发光性质。在77 K时,对于未配位的香豆素配体和金(I)衍生物,在所有情况下都能检测到磷光发射,在金(I)重原子存在的情况下更有利于磷光发射。这些化合物已被用作光敏剂以中等量子产率值产生单线态氧。

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