Phosphonate-functionalized heteroleptic ruthenium(II) bis(2,2′:6′,2″-terpyridine) complexes

Improved light absorbance does not lead to better DSC performance: studies on a ruthenium porphyrin–terpyridine conjugate

“…The relative integrals of these resonances compared to the aromatic region conrmed that no ester hydrolysis occurred during the complex formation; partial hydrolysis of PO(OEt) 2 -functionalized tpy ligands has been observed during the formation of some ruthenium(II) complexes. [36][37][38] The aromatic region of the [Ru(3)(4)][PF 6 ] 2 is shown in Fig. 1b and its signature is consistent with the presence of two different tpy domains.…”

Sticking and patching: tuning and anchoring cyclometallated ruthenium(ii) complexes

“…The reaction of cis-[Ru(bpy) 2 Cl 2 ] with H9 to give the diester [Ru(bpy) 2 ( 9)][PF 6 ] as the isolated product contrasts with the tendency of diethyl 2,2′:6′,2″-terpyridine-4′phosphonate to undergo partial hydrolysis to the monoester during formation of ruthenium(II) complexes. 18,19,21 X-ray quality single crystals of [Ru(bpy) 2 ( 7)][PF 6 ] were grown by diffusion of Et 2 O into a CH 2 Cl 2 solution of the compound. The octahedral tris(chelate) [Ru(bpy) 2 (7)] + is chiral, and as the complex crystallizes in the centrosymmetric space group P2 1 /n, both the Λand Δ-enantiomers are present in the lattice.…”

“…16 In the current work, we focus on a phosphonate ester rather than phosphonic acid-functionalized C^N ligand (Scheme 2). Hydrolytic deprotection of the ruthenium-bound diethyl phosphonates does not always proceed to completion [17][18][19][20][21] and phosphonate esters have been successfully used to modify TiO 2 surfaces, negating the need for this step. 22,23 5.16 mmol) was added and the reaction mixture heated at 110 °C for 90 min in a microwave reactor.…”

To deprotect or not to deprotect: Phosphonate ester versus phosphonic acid anchor ligands in copper(I)-based dye-sensitized solar cells

“…These phosphonic acids are prepared by hydrolytic deprotection of the ruthenium-bound diethyl phosphonates, but reaction may not proceed to completion, terminating at the corresponding monoester, depending on reaction conditions [14,15,17,18]. Partial hydrolysis of diester ligands can also occur during complexation of the ester-functionalized ligands with ruthenium(II) [16,19]. In the light of these observations, together with the empirically observed better solubility of the phosphonate esters compared to the phosphonic acids, we decided to investigate the use of phosphonate ester 2 (Scheme 1) as an anchoring ligand.…”