Adaptive Coordination-Driven Supramolecular Syntheses toward New Polymetallic Cu(I) Luminescent Assemblies

Abstract

A thermally activated delayed fluorescence (TADF) tetrametallic Cu(I) metallacycle A behaves as a conformationally adaptive preorganized precursor to afford, through straightforward and rational coordination-driven supramolecular processes, a variety of room-temperature solid-state luminescent polymetallic assemblies. Reacting various cyano-based building blocks with A, a homometallic Cu(I) 1D-helical coordination polymer C and CuM discrete circular heterobimetallic assemblies D (M = Ni, Pd, Pt) are obtained. Their luminescence behaviors are studied, revealing notably the crucial impact of the spin-orbit coupling offered by the central M metal center on the photophysical properties of the heterobimetallic D derivatives.

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

“…TbNIT-Ph-O-Hexyl also recalls similar structures with alkyl chains such as homochiral supramolecular subphthalocyanine columns, [18] a-cyclodextrin organic nanotubes, [19] or Cu I supramolecular helixes. [20] Additionally,t he chiral nature of the nanotubes makes TbNIT-Ph-O-Hexyl agood candidate to observe electric field modulation of magnetic exchange [21] or magneto-chiral dichroism [9b] as observed on NIT-based chains with 3d metal ions.C hiral Ln-NIT chain appears very appealing for the coexistence of strong spin-orbit coupling and frustrated magnetic interactions. [22] Last, TbNIT-Ph-O-Hexyl shows ah uge porosity (44 %o fcell volume) that opens the way to solvent or gas responsive SCMs with tuneable magnetic properties.T hese fluorinated and hydrophobic nanopores could also have original transport properties for gas or liquids as observed on nanometric lab-on-a chip devices.…”

Core-dependent properties of copper nanoclusters: valence-pure nanoclusters as NIR TADF emitters and mixed-valence ones as semiconductors

“…The blue-shiing trend with increasing temperature is suggestive of a TADF mechanism for Cu(I) clusters 1 and 2. 14 In this context, the temperature-dependent emission decay time was measured ( Fig. 3c and f), and their correlation was studied with the Boltzmann equation derived from the TADF model:…”

“…Initially, the comproportionation reaction furnished nanoclusters [Cu(I) 15 ( t BuC^C) 14 NO 3 ] (1) and [Cu(I) 28 ( t BuC^C) 22 (-SO 4 ) 2 (OMe) 2 ] (2). They were revealed to exhibit NIR photoluminescence mainly from the mixed alkynyl / Cu(I) LMCT and cluster-centered transition and further exhibit TADF.…”

Chiral Supramolecular Nanotubes of Single‐Chain Magnets

“…The stacking interaction between the β‐diketonate and the NIT phenyl ring may be the driving force for the creation of these screw chains. TbNIT‐Ph‐O‐Hexyl also recalls similar structures with alkyl chains such as homochiral supramolecular subphthalocyanine columns, α‐cyclodextrin organic nanotubes, or Cu I supramolecular helixes …”