Conglomerate, Racemate, and Achiral Crystals of Polymetallic Europium(III) Compounds of Bis- or Tris-β-diketonate Ligands and Circularly Polarized Luminescence Study

This work reports (a) conglomerate and racemic crystal structures of [(Δ,Δ,Δ,Δ,Δ,Δ)- or/and (Λ,Λ,Λ,Λ,Λ,Λ)-EuIII6(TTP)8(OH2)6Na4]n coordination polymers, (b) racemic crystal structures of (Δ,Δ,Δ,Δ)-/(Λ,Λ,Λ,Λ)-EuIII4(TTP)4(bipy)4(MEK)2(OH2)2 tetrahedral clusters, and (c) the achiral crystal structure of the [EuIII2(BTP)4(OH2)2Na2]n coordination polymer (where BTP = dianionic bis-β-diketonate, TTP = trianionic tris-β-diketonate, and bipy = 2,2′-bipyridine). The screw coordination arrangement of the TTP ligand has led to the formation of homoconfigurational racemic EuIII products. The conglomerate crystallization of [EuIII6(TTP)8(OH2)6Na4]n appears to be caused by the presence of the sodium, Na+ counterions, and interactions between oxygen atoms and the trifluoromethyl unit of the TTP ligand and Na+ ions. All the EuIII compounds exhibit characteristic red luminescence (5D0 → 7FJ, J = 0–4) in solution or in the solid crystalline state. Circularly polarized luminescence (CPL) was observed in the chiral EuIII6(TTP)8(OH2)6Na4]n species, displaying a |glum| value in the range of 0.15 to 0.68 at the 5D0 → 7F1 emission band. Subtle changes of the [EuIII6(TTP)8(OH2)6Na4]n structure which may be due to selection of twinned crystals or crystals that do not correspond to a perfect spontaneous resolution, are considered to be responsible for the variation in the observed CPL values

Excited State Engineering in Ag₂₉ Nanocluster through Peripheral Modification with Silver(I) Complexes for Bright Near-Infrared Photoluminescence

The optical property of an ionic metal nanocluster (NC) is affected by the ionic interaction with counter ions. Here, we report that the modification of trianionic [Ag29(BDT)12(TPP)4]3– NC (BDT: 1.3-benzenedithiol; TPP: triphenylphosphine) with silver(I) complexes led to the intense photoluminescence (PL) in the near-infrared (NIR) region. The binding of silver(I) complexes to the peripheral region of Ag29 NC is confirmed by the single-crystal X-ray diffraction (SCXRD) measurement, which is further supported by electrospray ionization mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR) spectroscopy. The change of excited-state dynamics by the binding of silver(I) complexes is discussed based on the results of a transient absorption study as well as temperature-dependent PL spectra and PL lifetime measurements. The modification of Ag29 NCs with cationic silver(I) complexes is considered to give rise to a triplet excited state responsible for the intense NIR PL. These findings also afford important insights into the origin of the PL mechanism as well as the possible light-driven motion in Ag29-based NCs