A Broadened Class of Donor-Acceptor Stacked Macrometallacyclic Adducts of Different Coinage Metals.
Zhou LuLorenzo LucianiShan LiVladimir N NesterovCristiano ZuccacciaAlceo MacchioniJacob L FrippWeijie ZhangMohammad A OmaryRossana GalassiPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2024)
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.
Keyphrases
- circulating tumor cells
- water soluble
- circulating tumor
- energy transfer
- mass spectrometry
- magnetic resonance
- cell free
- single molecule
- solar cells
- climate change
- ionic liquid
- molecular docking
- room temperature
- optical coherence tomography
- human health
- molecular dynamics simulations
- high speed
- drinking water
- capillary electrophoresis