Department of Organic Chemistry, Faculty of Chemistry, University of Łódź, Tamka 12, 91-403, Łódź, Poland.
Chemistry Department, Biological and Chemical Research Centre, University of Warsaw, ul. Żwirki i Wigury 101, 02-089, Warszawa, Poland.
Chemistry. 2019 Oct 11;25(57):13131-13145. doi: 10.1002/chem.201901101. Epub 2019 Aug 29.
The influence of the chemical substitution, crystal packing, and aurophilic interactions of the gold(I) acetylide complexes of the type (ArCOC≡C) AuPEt (n=1,2) on their luminescent properties were examined. All described complexes undergo ligand scrambling in solution, which results in the formation of stable, easily isolated crystals that contain [ArCO(C≡C) ] Au (Et P) Au homoleptic species. In particular, we observed that the (benzoylacetylide)gold(I) complex yields three crystal forms with strikingly different luminescence properties. We monitored the conversion pathway for these forms: an orange luminescent form of homoleptic complex upon drying undergoes spontaneous transformation to bright green fluorescent form and finally to the weakly blue emissive one. In addition, we report a rare example of a helical arrangement of Au⋅Au⋅Au chains that are observed for the first time in acetylide gold(I) complexes in the case of heteroleptic (benzoylacetylide)gold(I) complex. This is a very rare case in which crystal structures and ensuing electronic properties of the heteroleptic and Au complexes could be directly compared.
研究了（ArCOC≡C）AuPEt（n=1,2）型金（I）炔化物配合物的化学取代、晶体堆积和金键相互作用对其发光性质的影响。所有描述的配合物在溶液中都会发生配体交换，从而形成稳定、易于分离的晶体，其中包含[ArCO（C≡C）]Au（EtP）Au 同核物种。特别是，我们观察到（苯甲酰基乙炔）金（I）配合物生成三种具有显着不同发光性质的晶体形式。我们监测了这些形式的转化途径：干燥时，同核配合物的橙色发光形式会自发转化为明亮的绿色荧光形式，最后变为弱蓝色发射形式。此外，我们报告了一个罕见的例子，即 Au⋅Au⋅Au 链的螺旋排列，这在苯甲酰基乙炔金（I）配合物的情况下首次观察到。这是一个非常罕见的情况，其中可以直接比较异核和 Au 配合物的晶体结构和随之而来的电子性质。
