Syntheses, Photophysics, and Photochemistry of Trinuclear Copper(I) Thiolate and Hexanuclear Copper(I) Selenolate Complexes:  X-ray Crystal Structures of [Cu₆(μ-dppm)₄(μ₃-SePh)₄](BF₄)₂and [Cu₆{μ-(Ph₂P)₂NH}₄(μ₃-SePh)₄](BF₄)₂

Abstract

A series of trinuclear copper(I) thiolate complexes, [Cu(3)(mu-dppm)(3)(mu(3)-SR)(2)]BF(4) (R = C(6)H(4)Cl-4, C(6)H(4)CH(3)-4, C(6)H(4)OCH(3)-4, C(6)H(4)(OCH(3))(2)-3,4, C(6)H(4)-benzo-15-crown-5, or (t)()Bu), [Cu(3)(mu-dppm)(3)(mu(3)-S(t)()Bu)](BF(4))(2), and [Cu(3)(mu-dppm)(3)(mu(3)-SR)(mu(3)-Cl)]BF(4) (R = C(6)H(4)CH(3)-4, C(6)H(4)(t)()Bu-4, or C(6)H(4)(CH(3))(3)-2,4,6) and two hexanuclear copper(I) selenolate complexes, [Cu(6)(mu-P(wedge)P)(4)(mu(3)-SePh)(4)](BF(4))(2) (P(wedge)P = dppm, (Ph(2)P)(2)NH), have been synthesized, and their photophysical properties have been studied. The X-ray crystal structures of both copper(I) selenolate complexes have been determined. These complexes have been shown to exhibit long-lived low-energy emission in solution, attributed to an excited state of predominantly ligand-to-metal charge-transfer [chalcogenolate to copper(I)] origin.

Bis[μ-bis(diphenylphosphanyl)methane-κ2P:P′](μ-1-ethylthiourea-κ2S:S)bis[iodidocopper(I)] acetonitrile sesquisolvate

“…The dppm ligand and the bridging S atom of the ettu ligand force the two copper atoms into close proximity, leading to the formation of a close intramolecular Cu•••Cu contact [3.3747 (17) Å]. The Cu-P distances vary from 2.2563 (10) to 2.2786 (11) Å, which are quite similar to those observed in related copper(I) complexes containing the dppm ligand (Yam et al, 2001;Zhou et al, 2001). The Cu -S bond lengths (Cu1-S1 = 2.3450 (11), Cu2-S1 = 2.3493 (11) Å) are shorter than that found in for example [Cu 2 (µ-HL 1 ) 2 (µ-dppm)(η 1 -dppm) 2 ] (H 2 L 1 = 8-mercaptotheophylline), which are 2.392 (5)-2.410 (6) Å (Colacio et al, 1997).…”

“…For examples of dppm as a chelating ligand, see: Yang et al (2000); Liaw et al (2005); Jin et al (2009). For relevant examples of discrete complexes, see: Colacio et al (1997); Yam et al (2001); Zhou et al (2001); Nimthong et al (2008); Pakawatchai et al (2012). Table 1 Hydrogen-bond geometry (Å , ).…”

Crystal structure of (μ-N-allylthiourea-κ2S:S)bis[μ-bis(diphenylphosphanyl)methane-κ2P:P′]bis[bromidocopper(I)] acetonitrile disolvate

“…The CuÁ Á ÁCu distance in (I) is 3.3780 (7) Å , which is similar to the CuÁ Á ÁCu distance of 3.375 (2) Å in a copper(I) complex containing an S-bridging ligand and bidentate bridging dppm, [Cu 2 I 2 (C 3 H 8 N 2 S)(C 25 H 22 P 2 ) 2 ]Á1.5CH 3 CN (Nimthong et al, 2013) and much longer than 2.8 Å which is the sum of the van der Waals radii of the copper atoms (Yam et al, 2001). The Cu-P bond lengths in (I) ( Table 1) range from 2.2604 (8) to 2.2803 (8) Å and the Cu-S bond lengths of the bridges, 2.3543 (8) and 2.3520 (8) Å , are likewise similar to the those in the above mentioned complex [Cu-P = 2.2563 (10)-2.2786 (11) Å ; Cu-S = 2.3450 (11) and 2.3493 (11) Å ].…”

Binuclear Copper(I) Compounds with N‐Heterocyclic Thiolate and Diphosphane Ligands: Effects of Thiolate Ligands on Solid‐State Molecular Structures and Luminescence Properties

“…Reactions of copper(I) halides with N‐heterocyclic thiols or thiolates, in the presence of an arylphosphane, depending on the nature of thiol and phosphane, can result in different compounds exhibiting a variety of structural motifs . In an effort to further explore the ability of these systems to lead to the synthesis of novel Cu I complexes bearing a mixed set of S‐ and P‐donor atom ligands, we explored reactions of copper(I) halides, in the presence of a diphosphane (dppe), with three N‐heterocyclic thiolates that differ in their stereochemical and electronic properties, that is, the anions of mtdztH, ptztH, and tucH 2 cet (Scheme ).…”

“…In particular, N‐heterocyclic thiol/thiolate comprises a subclass of S‐donor ligands that can adopt a variety of coordination modes, acting either in their neutral or anionic forms: (a) in a monodentate fashion (through the S atom, or through the N atom), (b) as N,S‐chelating ligands, (c) as binuclear bridging ligands (through the S atom,, or the N and S atoms,) or (d) as trinuclear bridging ligands . Heteroleptic Cu I complexes incorporating S‐donor, N‐heterocyclic thiol/thiolate ligands, in combination with other types of ligands, such as P‐donor arylphosphanes, halides or N‐donor polypyridines, have been reported to exhibit diverse structures and interesting photophysical properties . In particular, the formation of specific structural motifs is strongly affected by the reaction/crystallization conditions as well as the electronic and steric properties of the thiol ligands.…”