A series of new dinuclear copper complexes with a tetraphosphane bridging ligand, [{(pz₄B)Cu}₂(µ-tpbz)] (1), [{(pz₂BH₂)Cu}₂(µ-tpbz)] (2), and [{(tz₂BH₂)Cu}₂(µ-tpbz)] (3) [tpbz = 1,2,4,5-tetrakis(diphenylphosphanyl)benzene, pz₄B = tetrakis(pyrazol-1-yl)borate, pz₂BH₂ = bis(pyrazol-1-yl)borohydrate, and tz₂BH₂ = bis(1,2,4-triazol-1-yl)borohydrate], have been synthesized and structurally characterized. The Cu^I atoms in these complexes are four-coordinate and adopt a tetrahedral coordination geometry. In each complex, the copper centers are bridged by a tpbz ligand and each Cu^I is further terminally chelated by a borate diimine anion. The central phenylene ring and the phosphine atoms of the tpbz ligand are essentially planar. The two Cu^I atoms in each molecule are located above and below the (P₂C₆H₂P₂) mean plane, respectively, leading to a chair-like conformation for the [Cu](P₂C₆H₂P₂)[Cu] fragment. The distances between the Cu^I atoms in each complex are about 8.7 Å. In the solid state, these complexes are emissive and exhibit yellow–orange photoluminescence [emission peaks, λ_max = 580 nm (1), 569 nm (2), 540 nm (3)] with lifetimes of 7.4–20.5 µs and quantum yields Φ = 0.07–0.45 at room temperature. Theoretical and experimental results indicate that these complexes have the lowest singlet (S₁) state and the lowest triplet (T₁) state with very close energy levels, and display thermally activated delayed fluorescence (TADF) at ambient temperature.

Hydrophobic metal-organic frameworks (MOFs) not only have high water stability, but also exhibit high adsorption capacity towards organic molecules, in particular hydrocarbons. Herein we report a rare metal fluoride organic framework MFOF-1 with high hydrophobicity, which is constructed from unprecedented fluoride- and sulfate-bridged cubane-type tetranuclear cobalt clusters. MFOF-1 consists of three types of polyhedral cages with face-sharing configurations, and possesses a novel (3,9)-connected 3D+3D3D self-interpenetrating array or the rare pyr topology. MFOF-1 shows high thermal stability and high stability in water and even acid/base aqueous solutions, and exhibits rather high H₂ and CO₂ storage capacities at ambient pressure. Remarkably, MFOF-1 shows little adsorption of water but considerably high uptakes of methanol, n-hexane, cyclohexane, and benzene, and exhibits a certain degree of adsorption selectivity of benzene over cyclohexane.

Two new metal–organic frameworks (MOFs) with novel architectures, namely, [Co₂(NDC)₂(H₂MDP)₂][(Co(NDC)(H₂MDP)] (1) and [Co(NDC)(H₂MDP)_0.5] (2) were synthesized through a one-pot reaction. The metal to ligand ratio was found to influence the formation of the two compounds, and their pure phases were successfully obtained only by adjusting the molar ratios of Co/H₂NDC/H₂MDP to be 1:1:1 and 2:2:1, respectively [H₂NDC = 1,4-naphthalenedicarboxylic acid, H₂MDP = methylenebis(3,5-dimethylpyrazole)]. X-ray crystallographic analyses showed that 1 crystallizes as a racemic twin and features an interesting threefold 3D/3D hetero-interpenetrating diamondoid framework with left-handed and right-handed helical chains, whereas 2 displays a 3D twofold homo-interpenetrating pcu network constructed from paddle-wheel secondary building units and H₂MDP pillars in a trans conformation. The one-pot synthesis of two or more MOFs with hetero-interpenetration and homo-interpenetration has been rarely reported.

Six heteroleptic cuprous complexes, [L¹Cu(PPh₃)₂](BF₄) (1a), [L¹Cu(DPEphos)](BF₄) (1b), [L²Cu(PPh₃)₂](BF₄) (2a), [L²Cu(DPEphos)](BF₄) (2b), [L³Cu(PPh₃)₂](BF₄) (3a), and [L³Cu(DPEphos)](BF₄) (3b) {L¹ = diphenyl(2-pyridyl)phosphane oxide, L² = diphenyl(8-quinolyl)phosphane oxide, L³ = diphenyl(2-pyridylmethyl)phosphane oxide, DPEphos = bis[2-(diphenylphosphanyl)phenyl] ether}, were prepared and fully characterized. The electronic absorption spectra and quantum chemical calculations indicate that the lowest excited states of these complexes can be assigned to the metal-to-ligand charge transfer (MLCT) transition. In poly(methyl methacrylate) (PMMA) films, these complexes exhibit blue-green to orange emissions with long lifetimes ranging from 7.5 to 28.6 μs. With wide energy-band gaps of 3.50 and 3.28 eV, complexes 3a and 3b emit efficiently in 20 wt.-% PMMA films with photoluminescence quantum efficiencies of 0.69 and 0.72, and emission maxima at 477 nm and 495 nm, respectively. Electroluminescent devices were fabricated with these N,O-based Cu^I complexes as emitters. The best device performance, with a peak current efficiency of 4.9 cd/A, was obtained for 3b.