Triangular tricopper(i) clusters supported by donor-substituted triazacyclohexanes

Abstract

Triazacyclohexanes (R(3)TAC,1a-i ) with pyridyl or thioether functionalities (R) in the N-substituents react with three equivalents of CuX (X = Cl (2), Br (3) or I (4)) in MeCN to give the triangular tri-copper clusters [R(3)TAC(CuX)(3)] (R = 2-pyridylmethyl (2a, 3a ), 5-(t)butyl-2-pyridyl (3b). 2-(3-phenylpropylthio)ethyl (3c), 2-(2-ethyl-butylthio)ethyl (3d), 2-(4-heptylthio)ethyl (2e, 3e ), 2-(1-heptylthio)ethyl (3f), 2-(2,4,6-trimethyl-benzylthio)ethyl (3g), 2-(o-methyl-benzylthio)ethyl (3h) and 2-(o-fluoro-benzylthio)ethyl (2i, 3i 4i)). The thioether complexes are stable towards air and water. The bromide bridge in the clusters can be replaced by chloride (2c, e, f, i) or iodide (4c, e, f, i ) by the reaction of a dichloromethane solution of the cluster with aqueous NaI or AgCl, respectively. Crystal structures of 2a, 3a, 3b, 2e, 3h and show triangular halide-bridged Cu(3) clusters capped by the triazacyclohexane and stabilised by the coordination of one pyridyl or thioether arm to each copper atom. DFT calculations confirm the NMR assignments and reveal the electronic structure of the copper triangle.

Isolation of chloride- and hydride-bridged tri-iron and -zinc clusters in a tris(β-oxo-δ-diimine) cyclophane ligand

“…The average result together with the solution C 3v symmetry deduced from our 1 H NMR data affords a chair-shaped [Fe 3 Cl 3 ] 3+ cluster within the internal cavity of the cyclophane. This chair motif has substantial precedent in d-block chemistry with analogous [M 3 Cl 3 ] n+ -type clusters have been reported for rhodium, [30][31][32] platinum, 33,34 copper, 35,36 and palladium. 37 However, to our knowledge based on search of the Cambridge Structural Database, this complex represents the first case of crystallographic structure of chair-shaped triiron cluster bridged by chlorides.…”

Organo Chalcogenone-Triggered Luminescent Copper(I) Clusters for Light Emitting Applications

“…The three Cu···Cu interactions in the clusters and distances are 2.634(7) Å (Cu1–Cu3), 2.702(8) Å (Cu1–Cu2), and 2.885(8) Å (Cu2–Cu3). The Cu1–Cu3 [2.634(7) Å] distance is longer than the reported Cu 3 Br 3 cluster with phenanthroline [2.552(13) Å] or tris­[2-2-pyridylethyl] phosphine ligand (2.480–2.570 Å) and is shorter than those in the Cu 3 Br 3 cluster with bidentate dtbdp [2.678(8)–2.978(8) Å], pyridyl methyl triazacyclohexane [2.800(7)–2.890(10) Å], and 1,3-dithines (2.819–3.249 Å) . All three copper­(I) atoms adopted a distorted tetrahedral geometry.…”

Self‐Assembly of Discrete Copper(I)‐Halide Complexes with Diacylthioureas

“…A similar Cu 3 I 3 ring was furnished by triazacyclohexane ( R 3 TAC) bearing three thioether functionalities ( R ), where each copper atom is bound to two bromide bridges, one nitrogen and one sulfur atom. In the current case, benefiting from the large S ··· S separation in L 3 , the Cu 3 I 3 ring in 10 is more stretched and spread, as indicated by the wider Cu–I–Cu angles (about 102°) and longer Cu ··· Cu distances (about 4.1 Å), when compared to those counterparts in R 3 TAC(CuI) 3 (about 68° and 2.9 Å) . In the packing diagram, each molecule of 10 has four direct neighbors to construct the three‐dimensional grids by four intermolecular N–H ··· O hydrogen bonds (Figure S16, Supporting Information).…”