5 years ago

Cupriphication of gold to sensitize d10-d10 metal-metal bonds and near-unity phosphorescence quantum yields [Chemistry]

Cupriphication of gold to sensitize d10-d10 metal-metal bonds and near-unity phosphorescence quantum yields [Chemistry]
Brooke M. Otten, Joshua F. Ivy, Rossana Galassi, Roy N. McDougald Jr., Lee M. Daniels, Dieaa Alhmoud, Mohammad A. Omary, Abdel-Monem M. Rawashdeh, Ruaa M. Almotawa, Simone Ricci, Eric W. Reinheimer, Mukunda M. Ghimire, Vladimir N. Nesterov, Alfredo Burini

Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reduction upon cupriphication of cyclic trinuclear trigonal-planar gold(I) complexes are found to sensitize ground-state Cu(I)–Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C2,N3-EtIm)4Cu2(µ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C2,N3-BzIm)2Cu(µ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C2,N3-MeIm)2Cu(µ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C2,N3-MeIm)Cu2(µ-3,5-(CF3)2Pz)2], (3b) and [Au(μ-C2,N3-EtIm)Cu2(µ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C2,N3-BzIm)]3[Cu(µ-3,5-(CF3)2Pz)]3, (2)} form upon reacting Au3 {[Au(μ-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R = benzyl/methyl/ethyl = BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5-(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via two Au(I)⋯Cu(I) metallophilic interactions, whereas 4a exhibits a hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10–d10 polar-covalent bond with ligand-unassisted Cu(I)–Au(I) distances of 2.8750(8) Å each—the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a “metal–metal bond” vis-à-vis “metallophilic interaction.” Density-functional calculations estimate 35–43 kcal/mol binding energy, akin to typical M–M single-bond energies. Congruently, FTIR spectra of 4a show multiple far-IR bands within 65–200 cm−1, assignable to vCu-Au as validated by both the Harvey–Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilic sensitization in extinction coefficient and solid-state photoluminescence quantum yields approaching unity (ΦPL = 0.90–0.97 vs. 0–0.83 for Au3 and Cu3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications.

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.