Supramolecular Assembly of Molecular Rare-Earth–3,5-Dichlorobenzoic Acid–2,2′:6′,2″-Terpyridine Materials: Structural Systematics, Luminescence Properties, and Magnetic Behavior

Abstract

The syntheses and crystal structures of 16 new rare-earth (RE = La(3+)-Y(3+))-3,5-dichlorobenzoic acid-terpyridine molecular materials characterized via single-crystal and powder X-ray diffraction are reported. These 16 complexes consist of four unique structure types ranging from molecular dimers (La(3+) and Ce(3+)) to tetramers (Pr(3+)-Y(3+)) as one moves across the RE(3+) series. This structural evolution is accompanied by subsequent changes in modes of supramolecular assembly (halogen bonding, halogen-π, halogen-halogen, and π-π interactions). Solid-state visible and near-infrared lifetime measurements were performed on complexes 6 (Sm(3+)), 7 (Eu(3+)), 9 (Tb(3+)), 10 (Dy(3+)), 11 (Ho(3+)), 12 (Er(3+)), and 14 (Yb(3+)), and characteristic emission was observed for all complexes except 11. Lifetime data for 11, 12, and 14 suggest sensitization by the terpy antenna does occur in near-infrared systems, although not as efficiently as in the visible region. Additionally, direct current magnetic susceptibility measurements were taken for complexes 10 (Dy(3+)) and 12 (Er(3+)) and showed dominant ferromagnetic behavior.

Two Series of Lanthanide Coordination Polymers and Complexes with 4′‐Phenylterpyridine and their Luminescence Properties

“…Quantum yields of the Dy 3+ , Pr 3+ , Ho 3+ , and Tm 3+ products obtained could not be determined reliably due to low intensity of emission in the visible, and of Nd 3+ and Yb 3+ products due to emission in the NIR. However, the respective metal ion based emission lifetimes were also successfully determined for the Dy 3+ , Pr 3+ , Ho 3+ , Tm 3+ , and Yb 3+ products (Table ), which are also close to the values presented in the literature , …”

Crystal structures, thermal decomposition kinetics and thermodynamic properties of lanthanide Ho(III) complex with 2,5-dichlorobenzoic acid and 5,5′-dimethyl-2,2′-bipyridine

“…稀土配合物由于多样的结构和其在发光 [1] 、生物 医学 [ 2 ] 、磁性 [ 3 ] 、催化 [ 4 , 5 ] 、气体存储 [ 6 ] 、荧光探 针 [7,8] 、热化学 [9] 等领域的潜在应用而成为越来越多科 学工作者研究的热点. 因此, 设计合成结构新颖和性能 独特的稀土配合物已成为科研工作者的研究目标.…”

Dinuclear LnIII Complexes with 9‐Anthracenecarboxylate Showing Field‐Induced SMM and Visible/NIR Luminescence

“…On the other hand, chelating ligands could block two or three coordination sites per Ln III ion, thereby preventing potential polymerization . For this purpose, N‐donor species such as 2,2′‐bipyridine, 1,10‐phenanthroline, or 2,2′:6′,2′′‐terpyridine are ideal candidates …”