Donamaría Rocío, Lippolis Vito, López-de-Luzuriaga José M, Monge Miguel, Nieddu Mattia, Olmos M Elena
Departamento de Química, Universidad de la Rioja, Centro de Investigación en Síntesis Química (CISQ), Complejo Científico Tecnológico , 26004 Logroño, Spain.
Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari , S.S. 554 Bivio per Sestu, 09042 Monserrato, Cagliari, Italy.
Inorg Chem. 2017 Oct 16;56(20):12551-12563. doi: 10.1021/acs.inorgchem.7b02035. Epub 2017 Sep 26.
Reaction of the heterometallic complexes [{Au(CX)}Tl] (X = Cl, F) with equimolecular amounts of the N,S-mixed-donor crown ethers [12]aneNS or [12]aneNS affords the new Au(I)/Tl(I) derivatives [{Au(CCl)}{Tl(L)}][Au(CCl)] [L = [12]aneNS (1), [12]aneNS (2)], [{Au(CF)}Tl([12]aneNS)] (3), or [{Au(CF)}Tl([12]aneNS)] (4). These complexes display the same Au/Tl metal ratio, but different structural arrangements. While the chlorinated derivatives 1 and 2·2THF display an ionic structure, the crystal structure of 3 contains neutral tetranuclear AuTl units, and complex 4 displays a polymeric nature and is the only one that does not show unsupported Au···Tl interactions. The lack of this interaction is responsible for the absence of luminescence in this last case. The optical properties of 1 and 3 in the solid state have been studied experimentally and theoretically, concluding that their luminescence has its origin in the Au···Tl interactions, and this is also influenced by their number and strength. DFT and TD-DFT theoretical calculations on model systems of complexes 1, 3, and 4 have been carried out in order to confirm the origin of their luminescence or its absence, as well as to justify their emission energies in spite of their different solid state structures.
异金属配合物[{Au(CX)}Tl]（X = Cl，F）与等物质的量的N，S混合供体冠醚[12]aneNS或[12]aneNS反应，得到新的Au(I)/Tl(I)衍生物[{Au(CCl)}{Tl(L)}][Au(CCl)] [L = [12]aneNS (1)，[12]aneNS (2)]，[{Au(CF)}Tl([12]aneNS)] (3)，或[{Au(CF)}Tl([12]aneNS)] (4)。这些配合物具有相同的Au/Tl金属比，但结构排列不同。氯化衍生物1和2·2THF具有离子结构，而3的晶体结构包含中性四核AuTl单元，配合物4具有聚合物性质，并且是唯一不显示无支撑Au···Tl相互作用的配合物。在最后这种情况下，这种相互作用的缺乏导致了发光的缺失。对1和3在固态下的光学性质进行了实验和理论研究，得出它们的发光源于Au···Tl相互作用，并且这也受其数量和强度的影响。对配合物1、3和4的模型体系进行了DFT和TD-DFT理论计算，以确认它们发光或不发光的起源，以及尽管它们具有不同的固态结构，但仍能解释其发射能量的原因。
