Ion-Driven Self-Assembly of Lanthanide Bis-phthalocyaninates into Conductive Quasi-MOF Nanowires: an Approach toward Easily Recyclable Organic Electronics

Abstract

Controlled self-assembly and rapid disintegration of supramolecular nanowires is potentially useful for ecology-friendly organic electronics. Herein, a novel method exploiting the binding between crown-substituted double-decker lanthanide phthalocyaninates (ML2, M = Lu, Ce, Tb) and K+ ions is applied for the one-step fabrication of macroscopically long conductive one-dimensional quasi-metal–organic frameworks. Their properties are controlled by the size of the lanthanide ion guiding the assembly through either intra- or intermolecular interactions. A LuL2 linker with a small interdeck distance yields fully conjugated intermolecular-bonded K+–LuL2 nanowires with a thickness of 10–50 nm, a length of up to 50 μm, and a conductivity of up to 11.4 S cm–1, the highest among them being reported for phthalocyanine assemblies. The large size of CeL2 and TbL2 leads to the formation of mixed intra- and intermolecular K+–ML2 phases with poor electric properties. A field-assisted method is developed to deposit aligned conductive K+–LuL2 assemblies on solids. The solid-supported nanowires can be disintegrated into starting components in a good aprotic solvent for further recycling.

Rare-earth based tetrapyrrolic sandwiches: chemistry, materials and applications

“…39a). 451 Noteworthy, this possibility was envisaged in 1994 by Toupance et al in one of keystone papers on the construction of ionoelectronic materials based on crown-substituted phthalocyanines; however, experimental verification of this hypothesis was reported only in 2021.…”

Unexpected Supramolecular-Induced Redox Switching in Sandwich Gd Bisphthalocyaninate

“…In summary, it has been demonstrated that the large radius of the Gd(III) ion determines the intramolecular incorporation of potassium cations into the double-decker crown-substituted phthalocyaninate, in contrast to the Lu(III) double-decker. 62,65 Furthermore, we achieved the supramolecular controlled ligand reduction of the double-decker Gd phthalocyaninate and the formation of the reduced inclusion complex {Gd-[(15C5) 4 Pc 2−/2− ] 2 − •4K + } 3+ . The increased distance between the ligands due to the supramolecular inclusion of potassium cations facilitates the switching of the redox state of the phthalocyanine.…”

“…62,63,65 leads to a very high electron conductivity of the final material up to 11.4 S•cm −1 . 65 In contrast, a similar strategy for the middle lanthanides results in an electron conductivity that is 8 orders of magnitude lower. The reason for this difference has not been studied in detail, but our work reveals an important factor for that.…”

“…The introduction of substituents responsible for supramolecular assembly opens up new opportunities to organize phthalocyanine molecules in a specific way. ,− One of the brightest examples of such substituents are crown ethers, − which enable the cation-induced assembly of sandwich lanthanide complexes, leading to control of their functional properties. − Alkali cations with an ionic radius larger than the crown ether cavity can connect two adjacent molecules forming dimers ,− or longer oligomers − (Figure a,b). They can also integrate between decks of the same sandwich molecule, altering the coordination polyhedra of the lanthanide center (Figure c), if the deck-to-deck distance is large enough.…”

Thin Films of Lanthanide Stearates as Modifiers of the Q-Sense Device Sensor for Studying Insulin Adsorption

“…The use of this protein as a drug is still an extremely common procedure in improving the quality of life for patients with diabetes. The questions of searching for chromatographic methods for specific isolation and determination are still important. − Thin-film materials containing lanthanide atoms, as an example of nanotechnology, are actively used in many fields. − Also, materials containing lanthanide atoms are being actively studied as materials for bioorganic sensors, − including for determining the activity of insulin and analytical applications in the analysis of insulin content in complex systems. ,− Taking into account all of the problems associated with the production and application of such materials for proteomics, the purpose of this work is to demonstrate the possibility of using films containing lanthanide ions for insulin adsorption.…”