Assembly of Heteroleptic Copper Complexes with Silver Salts: From Discrete Trinuclear Complexes to Infinite Networks

Abstract

The use of heteroleptic copper complexes functionalized with two differentiated coordinating groups for the elaboration of heterometallic extended networks is presented. Two novel 5-phenyl-dipyrrin (dpm) ligands appended with an imidazole or a pyrazole function, dpm-imid and dpm-pz, have been prepared and used as ligands for the synthesis of a series of heteroleptic (acacR)Cu(dpm) complexes (acacH = acetylacetonate; acacCN = 3-cyanoacetylacetonate). The X-ray crystal structures of these complexes revealed that, albeit no particular association mode is observed for the acac capping ligand, one-dimensional networks are formed with the acacCN capping ligand. Whereas the imidazole peripheral ligand is coordinated to the copper center of a neighboring complex in the structure of (acacCN)Cu(dpm-imid), such an interaction is absent for the pyrazole appended derivative, (acacCN)Cu(dpm-pz), leading to an association mode involving the peripheral nitrile group of the acacCN ligand. Upon reaction of the imidazole functionalized complexes, (acac)Cu(dpm-imid) and (acacCN)Cu(dpm-imid), with silver salts, trinuclear species, {[(acacR)Cu(dpm-imid)](2)Ag}(+), are formed as a result of the coordination of the azole nitrogen atom of two copper complexes to the silver ion. As expected, in the case of (acac)Cu(dpm-imid), these species do not self-assemble into an extended network owing to the absence of a peripheral coordinating group. However, for the (acacCN)Cu(dpm-imid) complex, the trinuclear species are equipped with peripheral nitrile groups, thus allowing the binding of metal centers. Consequently, these species self-assemble into one-dimensional polymers with association modes varying with the nature of the anion present in the silver salt.

Luminescent Coordination Polymers Based on Self‐Assembled Cadmium Dipyrrin Complexes

“…General: Dipyrrins 1 – 4 were prepared as described previously 8b. 11f, 15 All solvents were dried according to standard procedures. Other reagents were obtained from commercial sources and used as received.…”

Design and Synthesis of Dipyrrin Complexes Bearing Unique Structures, Properties and Functions

“…24,25 Sheet like structures are anticipated to produce novel catalytic, electronic and photonic materials. 26 Sakamoto and co workers nicely illustrated how novel functions from nanosheets prepared using a bottom up approach could be realized.…”

Crystal structure of meso‐substituted pyrazolyl porphyrin complexes and their highly active catalyst for oxidation of alkylbenzenes

“…Design different porphyrins and metalloporphyrins provide a new strategy for seeking novel functional to catalyst. However, over the last few decades, many catalyst of porphyrins or metalloporphyrins have been reported with peripheral substitutes commonly being carboxyl, pyridine or imidazole groups, pyrazolyl‐functionalized porphyrins and the influence of coordination metal atoms in center of porphyrin ring on catalytic activity have rarely been reported.…”