Structural Diversity of Coordination Polymers Based on a Heterotopic Ligand: Cu(II)-Carboxylate vs Cu(I)-Thiolate

Abstract

Two copper(II)-carboxylate disulfide coordination polymers [Cu((OCPhS))(HO)] (1, 2) and one copper(I)-thiolate coordination polymer [Cu( p-SPhCOH)] (3) have been synthesized using either the 4-mercaptobenzoic acid (HSPhCOH) or the 4,4'-dithiodibenzoic acid ((SPhCOH)) as ligand. These three compounds were characterized by X-ray diffraction, IR, and thermogravimetric analyses. Compounds 1 and 2 are polymorphs with the presence, for both, of dinuclear paddle-wheel copper(II)-carboxylates. In 1, the adjacent dimeric Cu units are linked by two (OCPhS) ligands generating a cyclic loop chain, and in 2, each pair of Cu (II) atoms is linked by four ligands to create 2D networks, that are 2-fold interpenetrated. Compound 3 presents a lamellar structure, with an exceptional thermal and chemical stability, and exhibits intrinsic multiple emission between 485 and 660 nm. The different intensities of these bands generate a cyclic luminescence thermochromism from yellow to green to yellow.

Facile synthesis, precise species control and chemical transformation of highly conducting organic metal chalcogenides CuxBHT (BHT = benzenehexathiol; x = 3, 4, and 5.5)

“…Compared to common Cu 2+ sources, Cu(I) salts have a moderate reaction rate with organothiolates due to their more complicated d 10 chemistry. 24,25 Furthermore, BHT and Cu 2 O have poor solubility in reaction solvents, which reduces the reaction concentration and diffusion rate of precursors, thus resulting in improved crystallinity.…”

Rational and site-selective formation of coordination polymers consisting of d10 coinage metal ions with thiolate ligands using a metal ion-doped polymer substrate

“…1C and S2†); all peaks of the obtained samples were assigned to [Cu( p -SPhCOOH)] n CP peaks (simulation) and the halo pattern of polyimide. 8,9 Moreover, the sharp diffraction peaks of the obtained samples indicated that the obtained CPs consisted of [Cu( p -SPhCOOH)] n CPs with high crystallinity. The [Cu( p -SPhCOOH)] n CPs exhibited characteristics of ligand-to-metal charge transfer (LMCT) and ligand-to-metal–metal charge transfer (LMMCT).…”

“…The [Cu( p -SPhCOOH)] n CPs exhibited characteristics of ligand-to-metal charge transfer (LMCT) and ligand-to-metal–metal charge transfer (LMMCT). 9 To investigate the luminescence properties of the obtained composite material, the film was characterized by fluorescence spectrometry (Fig. S3 † ).…”

“…Herein, we demonstrate an interfacial synthetic approach for fabricating CPs comprising d 10 coinage metals and thiolates on polymer substrates. In this study, we selected a [Cu( p -SPhCOOH)] n , 9 [Ag( p -SPhCOOH)] n and mixed-metal [Cu x Ag 1− x ( p -SPhCOOH)] n CPs. 10 We employed the polyimide substrate bearing cation-exchangeable group by hydrolyzing alkali solutions for precursors and template for CP-based films ( Scheme 1 ).…”

Sustainable and Efficient Low‐Energy Light Emitters: A Series of One‐Dimensional d10 Coinage Metal–Organic Chalcogenolates, [M(o‐SPhCO2H)]n

“…They form extended 2D M(I)‐S networks and show interesting photophysical properties. For example, [Au( p ‐SPhCO 2 Me)] n CP has a bright yellow emission with a quantum yield (QY) as high as 70 % in solid state at room temperature, [7a] while some other compounds of this family have multiple emission peaks which evolve independently with temperature, resulting in thermoluminochromism [7b–e] …”