Lu Zhou, Luciani Lorenzo, Li Shan, Nesterov Vladimir N, Zuccaccia Cristiano, Macchioni Alceo, Fripp Jacob L, Zhang Weijie, Omary Mohammad A, Galassi Rossana
Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA.
School of Science and Technology, Chemistry Division, University of Camerino, ChIP Via Madonna delle Carceri, 10, I-62032, Camerino, Italy.
Chemistry. 2024 Sep 11;30(51):e202401576. doi: 10.1002/chem.202401576. Epub 2024 Jul 6.
A yet-outstanding supramolecular chemistry challenge is isolation of novel varieties of stacked complexes with finely-tuned donor-acceptor bonding and optoelectronic properties, as herein reported for binary adducts comprising two different cyclic trinuclear complexes (CTC@CTC'). Most previous attempts focused only on 1-2 factors among metal/ligand/substituent combinations, resulting in heterobimetallic complexes. Instead, here we show that, when all 3 factors are carefully considered, a broadened variety of CTC@CTC' stacked pairs with intuitively-enhanced intertrimer coordinate-covalent bonding strength and ligand-ligand/metal-ligand dispersion are attained (d 2.868(2) Å; ΔE>50 kcal/mol, an order of magnitude higher than aurophilic/metallophilic interactions). Significantly, CTC@CTC' pairs remain intact/strongly-bound even in solution (K 4.67×10 L/mol via NMR/UV-vis titrations), and the gas phase (mass spectrometry revealing molecular peaks for the entire CTC@CTC' units in sublimed samples), rather than simple co-crystal formation. Photo-/electro-luminescence studies unravel metal-centered phosphorescence useful for novel all metal-organic light-emitting diodes (MOLEDs) optoelectronic device concepts. This work manifests systematic design of supramolecular bonding and multi-faceted spectral properties of pure metal-organic macrometallacyclic donor/acceptor (inorganic/inorganic) stacks with remarkably-rich optoelectronic properties akin to well-established organic/organic and organic/inorganic analogues.
一个尚未解决的超分子化学挑战是分离出具有精细调节的供体-受体键合和光电性质的新型堆叠配合物，如本文报道的由两种不同的环状三核配合物（CTC@CTC'）组成的二元加合物。以前的大多数尝试只关注金属/配体/取代基组合中的1-2个因素，从而得到异双金属配合物。相反，我们在此表明，当仔细考虑所有三个因素时，可以获得各种各样的CTC@CTC'堆叠对，其三聚体间的配位共价键强度和配体-配体/金属-配体色散直观上得到增强（d = 2.868(2) Å；ΔE>50 kcal/mol，比亲金/亲金属相互作用高一个数量级）。值得注意的是，即使在溶液中（通过NMR/UV-vis滴定法测得K = 4.67×10 L/mol）和气相中（质谱显示升华样品中整个CTC@CTC'单元的分子峰），CTC@CTC'对仍保持完整/强结合，而不是简单的共晶形成。光致/电致发光研究揭示了以金属为中心的磷光，这对新型全金属有机发光二极管（MOLED）的光电器件概念很有用。这项工作体现了超分子键合的系统设计以及纯金属有机大环金属环供体/受体（无机/无机）堆叠的多方面光谱性质，其具有与成熟的有机/有机和有机/无机类似物相似的极其丰富的光电性质。
