A Broadened Class of Donor-Acceptor Stacked Macrometallacyclic Adducts of Different Coinage Metals.

Autor: Lu Z; Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA., Luciani L; School of Science and Technology, Chemistry Division, University of Camerino, ChIP Via Madonna delle Carceri, 10, I-62032, Camerino, Italy., Li S; Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA., Nesterov VN; Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA., Zuccaccia C; Department of Chemistry, Biology and Biotechnology, University of Perugia and CIRCC, Via Elce di Sotto 8, I-06123, Perugia, Italy., Macchioni A; Department of Chemistry, Biology and Biotechnology, University of Perugia and CIRCC, Via Elce di Sotto 8, I-06123, Perugia, Italy., Fripp JL; Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA., Zhang W; Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA., Omary MA; Department of Chemistry, University of North Texas, Denton, Texas, 76203, USA., Galassi R; School of Science and Technology, Chemistry Division, University of Camerino, ChIP Via Madonna delle Carceri, 10, I-62032, Camerino, Italy.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Sep 11; Vol. 30 (51), pp. e202401576. Date of Electronic Publication: 2024 Jul 06.
DOI: 10.1002/chem.202401576
Abstrakt: 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 M-M' 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 eq 4.67×10 5  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.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE
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