Design of pure heterodinuclear lanthanoid cryptate complexes

Abstract

Heterolanthanide complexes are difficult to synthesize owing to the similar chemistry of the lanthanide ions. Consequently, very few purely heterolanthanide complexes have been synthesized. This is despite the fact that...

Stoichiometrically Controlled Assembly of Lanthanide Molecular Complexes of the Heteroditopic Divergent Ligand 4′-(4-Pyridyl)-2,2′:6′,2″-terpyridine N-Oxide in Hypodentate or Bridging Coordination Modes. Structural, Magnetic, and Photoluminescence Studies

“…53−55 Furthermore, very little attention has been paid in the literature to the analogue Noxidated ligand 4′-(4″′-pyridyl-N-oxide)-2:2′,6′:2″-terpyridine (pyterpyNO) (Scheme 1); a single paper reported the synthesis of a mononuclear iron(II) complex, [Fe-(pyterpyNO) 2 ](BF 4 ) 2 , where the metal is coordinated to only the terpyridine unit. 56 Nevertheless, this rigid aromatic ligand with two different binding sites is expected to have a rich coordination chemistry, to be able to control the selective and spontaneous organization of molecular units into ordered structures, and to be potentially useful for the synthesis of heterometallic complexes, a hot topic in the development of polynuclear molecular materials based on lanthanide systems, 57 as previously shown for the analogous 4,4′-bipyridine N-oxide ligand. 23,35−37 In this work, we show that pyterpyNO can bridge two rareearth centers in a hypodentate mode through the oxygen atom.…”

“…A terpyridyl unit is often used in the design of new organic linkers for the relatively easy synthesis and functionalization, for the strong bond with d transition metals, and for the interesting redox, photoluminescent, and magnetic properties. − The divergent ligand 4′-(4″′-pyridyl)-2:2′,6′:2″-terpyridine (pyterpy) is well-known in the literature, forming a large number of molecular and extended structure compounds for d metals − but a limited number of examples for lanthanide metals. − Furthermore, very little attention has been paid in the literature to the analogue N-oxidated ligand 4′-(4″′-pyridyl- N -oxide)-2:2′,6′:2″-terpyridine (pyterpyNO) (Scheme ); a single paper reported the synthesis of a mononuclear iron­(II) complex, [Fe­(pyterpyNO) 2 ]­(BF 4 ) 2 , where the metal is coordinated to only the terpyridine unit . Nevertheless, this rigid aromatic ligand with two different binding sites is expected to have a rich coordination chemistry, to be able to control the selective and spontaneous organization of molecular units into ordered structures, and to be potentially useful for the synthesis of heterometallic complexes, a hot topic in the development of polynuclear molecular materials based on lanthanide systems, as previously shown for the analogous 4,4′-bipyridine N -oxide ligand. ,− …”

Designed polynuclear lanthanide complexes for quantum information processing

“…[67][68][69] The alternative way to obtain heterometallic compounds of high site-selectivity is through consecutive synthetic steps, thus sequentially positioning each Ln ion. [70][71][72][73][74][75] This strategy allows involves also binding two or more Ln discrete compounds, thus obtaining multinuclear complexes featuring two 76,77 or three 78,79 different 4f ions. The main drawback of these methods is that they are tedious and challenging synthetically, preventing the screening of many Ln combinations, the production of sufficient amounts for physical studies or implementations, the preparation of magnetically dilute materials or repeated attempts to grow large single crystals.…”

Unparalleled selectivity and electronic structure of heterometallic [LnLn′Ln] molecules as 3-qubit quantum gates

“…20 Most reported heterometallic lanthanide molecules have been obtained following multistep procedures where the different metals are incorporated sequentially. 8,9,[21][22][23][24][25] On the other hand, methods enabling the selective distribution of metals thermodynamically, despite being more desirable, are very scarce. The reason is that their 4f electrons are highly shielded by occupied 5s and 5p shells, thus hampering the segregation of lanthanides based on chemical reactivity.…”