The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

Abstract

aWe report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes.We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione ( pd), which has selective N,N' or O,O' binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)

The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry

“…Likewise, the C5-C6 bond distance of 1.456(5) Å in 1, is shorter than the C-C single bond in pd 0 (1.54(6) Å), but longer than the C-C double bond in pd 2À (1.38(2) Å). 13 These data are also in good agreement with the metrics obtained from DFT calculations (vide infra).…”

“…[9][10][11][12] We also recently reported heterometallic rare earth-transition metal complexes utilising pd as a template. 13 Our two-step route was necessary because although pd is reported to react with a number of reducing agents, the products are insoluble in common solvents, precluding collection of spectroscopic data and definitive assignment of redox state, but more importantly further reactivity. 11,14,15 In contrast to the well-developed chemistry of transition metal semiquinones, 16 there are only three reports of the in situ characterisation of pd À .…”

Dysprosium Single-Molecule Magnets Involving 1,10-Phenantroline-5,6-dione Ligand

“…Its electro-activity could be exploited to modulate the physical properties as a function of its oxidation state, i.e., to design redox magnetic and photo-emissive switches, as already published with other redox-active ligands [31][32][33]. The L ligand was employed to design both pure 4f [34][35][36][37][38][39] and hetero-bimetallic nd4f [40][41][42] coordination complexes to study their biological activities and photo-physical properties. It is worth noting that the elaboration of hetero-bimetallic compounds implies the reduction of the ligand in its 5,6-dihydroxy-1,10-phenantroline form.…”

Influence of a Lanthanide Ion on the Ni Site of a Heterobimetallic 3d–4f Mabiq Complex

“…[34][35][36] Despite the number of reports with either 3d or 4f centers in combination with redox-active ligands, complexes comprising all three groups are surprisingly limited. [37][38][39][40] Given the evidence for improved magnetic properties in systems with two paramagnetic centers, synthesizing 3d-4f systems comprising redox-active ligands -in which a ligand radical can exist alongside a paramagnetic lanthanide -offers further opportunities to modulate and exploit exchange interactions. An example is the study by Goudy et.…”