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Reaction of [Au(tht)2](ClO4) (tht = tetrahydrothiophene), [Cu(CH3CN)4](ClO4), 3,6-di-tert-butyl-1,8-diethynyl-9H-carbazole (H3decz), and bis(2-diphenylphosphinophenyl)ether (POP) in the presence of triethylamine (NEt3) gave the cluster complex Au4Cu2(decz)2(POP)2 as yellow crystals. As revealed by X-ray crystallography, the Au4Cu2 cluster exhibits scissor-like structure sustained by two decz and two POP ligands and stabilized by Au-Cu and Au-Au interactions. The Au4Cu2 cluster shows bright yellow to orange photoluminescence upon irradiation at >300 nm, arising from 3[π (decz)→5d (Au)] 3LMCT (ligand-to-metal charge transfer) and 3[π→π* (decz)] 3IL (intraligand) triplet states as revealed by theoretical and computational studies. When it is mechanically ground, reversible phosphorescence conversion from yellow to red is observed owing to more compact molecular packing and thus stronger intermetallic interaction. Variable-temperature luminescence studies reveal that it displays distinct red-shifts of the emission whether the temperature is elevated or lowered from ambient temperature, suggestive of exceptional thermochromic phosphorescence characteristics. [ABSTRACT FROM AUTHOR]

Two heteroctanuclear Au4Ag4 cluster complexes of 4,5-diethynylacridin-9-one (H2L) were prepared through the self-assembly reactions of [Au(tht)2](CF3SO3), Ag(tht)(CF3SO3), H2L and PPh3 or PPh2Py (2-(diphenylphosphino)pyridine). The Au4Ag4 cluster consists of a [Au4L4]4− and four [Ag(PPh3)]+ or [Ag(PPh2Py)]+ units with Au4L4 framework exhibiting a twisted paper clip structure. In CH2Cl2 solutions at ambient temperature, both compounds show ligand fluorescence at ca. 463 nm as well as phosphorescence at 650 nm for 1 and 630 nm for 2 resulting from admixture of 3IL (intraligand) of L ligand, 3LMCT (from L ligand to Au4Ag4) and 3MC (metal-cluster) triplet states. Crystals or crystalline powders manifest bright yellow-green phosphorescence with vibronic-structured emission bands at 530 (568sh) nm for complex 1 and 536 (576sh) nm for complex 2. Upon mechanical grinding, yellow-green emission in the crystalline state is dramatically converted to red luminescence centered at ca. 610 nm with a drastic redshift of the emission after crystal packing is destroyed. [ABSTRACT FROM AUTHOR]

A dpppy-protected (dpppy = 2,6-bis(diphenylphosphino)pyridine) d10–d10 heterooctanuclear cluster complex [Ag3Cu5(ebzcz)6(dpppy)3](ClO4)2 (Hebzcz = 1-(3,6-di-tert-butylcarbazol-9-yl)-4-ethynylbenzene) was prepared by self-assembly reaction and characterized by single crystal X-ray diffraction. The diphosphine-supported Ag3Cu5 cluster structure is highly stabilized through substantial Cu–Ag and Cu–Cu intermetallic interactions. Since the Ag3Cu5 cluster is sufficiently shielded by bulky ligands (three ebzcz and three dpppy), thermally non-radiative relaxation is strongly prohibited so as to give brilliant photoluminescence under ambient conditions. As revealed by TD-DFT studies, the luminescence arises from metal cluster-centred 3[d → p/s] and 3[π (ebzcz) → π* (dpppy)] 3LLCT (ligand-to-ligand charge transfer) transitions. Taking advantage of Ag3Cu5 cluster complex as a phosphorescent dopant, a high-efficiency solution-processed organic light-emitting diode is achieved with a peak current efficiency of 38.1 cd A−1, a power efficiency of 29.9 lm W−1 and an external quantum efficiency of 14.7%. [ABSTRACT FROM AUTHOR]

A feasible synthetic approach to achieve Ag8, Ag16 and Ag29 silver(i) nanoclusters is reported by the use of 1,8-diethynyl-9H-carbazole (H3decz) as a directing ligand. The silver(i) nanoclusters exhibit room-temperature photoluminescence in both solution and solid state. The emission band shows stepwise red-shifts from visible to near-infrared region with the increase of cluster nuclearity following 2 (Ag8, λem = 571 nm) →3 (Ag16, λem = 651 nm) →4 (Ag29, λem = 916 and 875sh nm) in fluid CH2Cl2. [ABSTRACT FROM AUTHOR]