Luminescent vapochromic single crystal to single crystal transition in one-dimensional coordination polymer featuring the first Cu(i) dimer bridged by an aqua ligand

Abstract

The reaction of the pre-assembled bimetallic Cu(I) [Cu2(2-dppm)2]2+ fragment with the ligand 1,4-dicyanobenzene B0 in non-distillated CH2Cl2 allows the characterisation of an unexpected one-dimensional coordination polymer D, while no reaction...

Straightforward coordination-driven supramolecular chemistry preparation of a discrete solid-state luminescent Cu4 polymetallic compact assembly based on conformationally flexible building blocks

“…Therefore, the self-assembly CDS processes occurring during the association of the partially flexible ditopic linker L3 with the pre-assembled precursor [Cu2(2-dppm)2] lead to the formation of a discrete tetrametallic assembly D that resembles the architecture observed in B (Scheme 1), 13 and do not afford a 1D-CP such as the C (Scheme 1). 14 During these CDS processes, the ligand L3 presents thus a behavior that is significantly similar to what is observed with the fully aliphatic flexible linker L1 and is in a marked contrast with the results obtained with the rigid aromatic linker L2. The introduction within the backbone of these nitrile-capped ditopic linkers of only a limited amount of methylene units can have therefore a critical impact on the fate of the self-assembly CDS processes conducted upon their coordination on the conformationally flexible [Cu2(2-dppm)2] pre-assembled unit.…”

“…Recently, this study was extended to the reaction of the 1,4-dicyanobenzene ditopic linker L2 (Scheme 1) with the [Cu2(2-dppm)2] 2+ fragment, affording the one-dimensional coordination polymer (1D-CP) C that presents in its repetition unit the first Cu(I) bimetallic unit in which a water molecule bridges two Cu(I) metal centers. 14 This 1D-CP exhibits reversible solid-state luminescence vapochromism properties due to unique single-crystal to single-crystal transitions caused by the adsorption in the bulk crystals of volatile and mobile solvents vapors.…”

“…Within the [Cu2(2-dppm)2] bimetallic sub-units, an intermetallic distance of 3.33 Å is observed, precluding therefore metallophilic interactions within D while, altogether, the other metric parameters of the [Cu2(2-dppm)2] units are very similar to those observed in the polymetallic assemblies previously described bearing such bimetallic fragment. [11][12][13][14] This intermetallic distance in D is similar to the value found in B (d(Cu-Cu) = 3.33 Å) 13 in which the metal centers coordination in the same than in D but is larger than in C (d(Cu-Cu) = 3.13 Å) 14 where a bridging aqua ligand is observed between the metal centers of the [Cu2(2-dppm)2] bimetallic subunits. In the bulk crystal, derivatives D are isolated supramolecular assemblies that do not share specific short contact intermolecular interactions.…”

“…Importantly, such an organization is also favoured by the conformational flexibility of the [Cu2(2-dppm)2] 2+ sub-units (facile variation of the intermetallic distance and the coordination number of the metal ions without collapse of the [Cu2(2-dppm)2] core). Scheme 1: Synthesis of derivative B 13 , C 14…”

Coordination‐Driven Supramolecular Synthesis Based on Bimetallic Cu(I) Precursors: Adaptive Behavior and Luminescence

“…They are also mandatory in order to achieve the transfer of these new synthetic outcomes toward concrete technological applications, since they will contribute for the set‐up of controlled and reproducible procedures to prepare devices in which the specifies of the Cu(I)‐based supramolecular assemblies will be taken advantage of. So far, the characterized supramolecular Cu(I) assemblies present various luminescence properties supplying new source for emissive derivatives that may deserve general interest not only as innovative emitters for lighting applications such as in OLEDs but also as new sources of stimuli responsive multifunctional luminescent materials [15c,34] . Indeed, the large flexibility and lability of the Cu(I) ion coordination sphere render the gross conformation of such Cu(I) species potentially very sensitive to external stimuli, which concomitantly may induce alteration of their photophysical properties.…”