Homoleptic Luminescent Lanthanide Frameworks with the Tricyanohydridoborate Anion

Cyanoborates

“…[Co(bpy) 3 ][BH(CN) 3 ] 2 , [Co(bpy) 3 ][BH(CN) 3 ] 3 (bpy = 2,2′‐bipyridyl), which were tested as redox‐shuttles in DSSCs , . The coordination polymers 3 ∞[ Ln {BH(CN) 3 } 3 ] [ Ln = Eu, Tb] were synthesized from the respective lanthanide chloride and (H 3 O)[BH(CN) 3 ] in acetonitrile and their photoluminescence properties were studied . EMIm‐ MHB was successfully tested as a component of electrolytes for semi‐transparent photovoltaic cells for blue optoelectronic devices and in DSSCs.…”

Lanthanide Coordination Polymers and MOFs based on the Dicyanodihydridoborate Anion

“…Thus, it was possible to synthesize a range of different tetracyanoborates with transition metal and lanthanide cations . Closely related to the [B(CN) 4 ] − anion is the [BH(CN) 3 ] − anion, which is also known to form manifold coordination compounds with transition metals, as well as lanthanides . Further substitution of a cyano group with hydrogen leads to the anion [BH 2 (CN) 2 ] − , which was first described with main group element cations as counter ions .…”

“…[8] Closely related to the [B(CN) 4 ] À anion is the [BH(CN) 3 ] À anion,w hich is also known to form manifold coordination compounds with transition metals, [9] as well as lanthanides. [10] Further substitution of ac yano group with hydrogen leads to the anion[ BH 2 (CN) 2 ] À , which was first describedw ith main group elementc ations as counter ions. [9,11] Although the [BH 2 (CN) 2 ] À anion is also used as component of ionic liquids, [1a, 12] there is not much known abouti ts coordinationc hemistry besides the aforementioned compounds.…”

“…[18] Both cyanoborates andd initriles can be utilized as suitable linkersf or lanthanide coordination compounds giving access to new compounds ranging from one-dimensional up to three-dimensional coordination polymers. [10,[15][16][17][18][19] The most evident differenceb etweent hese ligands is their electronic character,a sc yanoborates are anions, acting not only as linker but also assuring chargec ompensation of the Ln 3 + ions, whereas the neutrald initrilesa re donor ligandsa nd requirea dditional components like chloride ions for chargec ompensation. Despite these differences, both mentioned ligand types can be used to unlock lanthanide luminescence in the obtained products.…”

“…Coordination of cyano groups to lanthanide cations can also be observed when dinitriles such as 1,3‐C 6 H 4 (CN) 2 and 1,4‐C 6 H 4 (CN) 2 are used, leading to the closely related products 3 ∞ [LnCl 3 {1,3‐C 6 H 4 (CN) 2 }] (Ln=Eu, Tb, Ho) and 3 ∞ [LnCl 3 {1,4‐C 6 H 4 (CN) 2 }] (Ln=Sm, Gd, Tb, Y) . Both cyanoborates and dinitriles can be utilized as suitable linkers for lanthanide coordination compounds giving access to new compounds ranging from one‐dimensional up to three‐dimensional coordination polymers . The most evident difference between these ligands is their electronic character, as cyanoborates are anions, acting not only as linker but also assuring charge compensation of the Ln 3+ ions, whereas the neutral dinitriles are donor ligands and require additional components like chloride ions for charge compensation.…”