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

Abstract

Pre‐organized adaptive Cu(I) bimetallic precursors can be successfully engaged in coordination‐driven supramolecular reactions. Selective formation either of a large family of compact metallacycles or of polymetallic discrete assemblies and one‐dimensional coordination polymers is rationalized taking into account the relative amplitudes of conformational flexibility allowed by the precursors used. It reveals the originality of the self‐assembly processes conducted with such Cu(I)‐based building blocks. In addition, exalted luminescence properties can be embedded in the resulting supramolecular assemblies due to the specific photophysical behaviors of Cu(I)‐luminophores. General and straightforward access toward coordination‐driven supramolecular assemblies featuring original architectures and multifunctional luminescence properties is therefore highlighted, taking advantage of both the specificities of the coordination chemistry and the electronic structure of derivatives based on the Cu(I) ion.

Chain Length Effect on the Structural and Emission Properties of the CuI/Bis((4-methoxyphenyl)thio)alkane Coordination Polymers

“…Since the pioneer works by Hardt and Holdt in the late 70s − and later by Ford and his collaborators in the 80s on neutral copper­(I) halide clusters Cu x X x L y (X = I; 2, 4, y = 4), this chemistry has been extended to a larger family of Cu x X x L y -containing complexes and coordination polymers (CP; X = Cl, Br, I, OH; 2 < x < 8, y = 4...). − This field is largely dominated by N- and P-donor ligands, and significant advances in the field of material science have been made. − In particular, when X = I, for the clusters, namely the closed-cubane Cu 4 I 4 , the resulting responsive materials turn out to be strongly emissive, and properties such as vapo-, solvato-, mechano-, and thermochromism have been reported. ,,− The effect of the aliphatic chain length variation that connects two NC/P-donor units with ditopic linkers on the outcomes of their coordination chemistry on coinage metal ions was also previously studied. − …”

A family of CuI-based 1D polymers showing colorful short-lived TADF and phosphorescence induced by photo- and X-ray irradiation

“…The luminescent copper(I) complexes are attracting everincreasing interest due to their unique photophysical properties, great structural diversity, low cost, accessibility and eco-friendliness. [1][2][3][4][5][6][7][8][9][10][11][12] These compounds can generate excited states of metal-to-ligand charge transfer (MLCT) type, allowing the manifestation of efficient phosphorescence and/or thermally activated delayed fluorescence (TADF) at ambient temperature. [13][14][15] Polynuclear complexes with Cu⋯Cu short contacts can also exhibit cluster-centered phosphorescence ( 3 CC).…”

TADF and X-ray Radioluminescence of New Cu(I) Halide Complexes: Different Halide Effects on These Processes

“…Metal halide complexes continue to attract ever-increasing attention because of their remarkable functional properties, stability, and facile synthesis [ 1 , 2 , 3 , 4 ]. Especially promising are Cu(I) halide complexes featuring intriguing luminescent properties as well as rich structural diversity, various molecular complexity, and robustness [ 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 , 14 ]. It is well known that upon excitation, the Cu(I) complexes supported by C-, N-, P-, S-, and As-donating ligands can generate the excited states of metal-to-ligand charge transfer type (MLCT) [ 15 , 16 ].…”