4′-Functionalized 2,2′:6′,2″-terpyridines as the NˆN domain in [Ir(CˆN)2(NˆN)][PF6] complexes

Abstract

The cyclometallated iridium(III) complexes [Ir(ppy)2(N^N)][PF6] (Hppy = 2phenylpyridine) with N^N = 4'-chloro-2,2':6',2"-terpyridine (1), 4'-methoxy-2,2':6',2"terpyridine (2), 4'-ethoxy-2,2':6',2"-terpyridine (3), 4'-methylthio-2,2':6',2"-terpyridine (4), 4'-phenylthio-2,2':6',2"-terpyridine (5) and 4'-dimethylamino-2,2':6',2"-terpyridine (6) are reported including the single crystal structures of 2{[Ir(ppy)2(1)][PF6]}. 0.6Et2O. CH2Cl2, [Ir(ppy)2(5)][PF6]. 0.5CH2Cl2 and [Ir(ppy)2(6)][PF6]. The single crystal structure of [Ir(ppy)2(3)]Cl. 2H2O. MeCN is also reported. In each complex, the 2,2':6',2"-terpyridine (tpy) ligand binds to the metal centre in a bidentate fashion with the non-coordinated pyridine ring folded into the coordination sphere and engaging in a pyridine-phenyl π-stacking interaction. Solution NMR spectra are consistent with hindered rotation of the non-coordinated pyridine ring at 298 K, with intra-cation CH...N(pyridine) hydrogen bond formation between adjacent

Cytotoxic Activities of Bis‐cyclometalated Iridium(III) Complexes Containing Chloro‐substituted κ2N‐terpyridines

“…[12] Thus, the three important bond angles in the central core of 1 (compare caption in Figure 1) agree very well with the reported corresponding ones for [Ir(ppy) 2 (k 2 N-terpy-Cl)] + : N6À Ir2À N7, 76.40 (15); N9À Ir2À C63, 80.19 (16) and N10À Ir2À C74, 81.12(18). [12] The IrÀ N and IrÀ C bond parameters within the cyclometalated chelating ring systems were in good accordance with the usually observed ones in related compounds reported by us. [11] Compound 2 crystallized from a dichloromethane/methanol/ iso-hexane mixture in the triclinic space group P À 1 with four molecules in the unit cell.…”

“…The coordination sphere of the cation in 1 is best comparable with that of the known complex [Ir(ppy) 2 (k 2 N-terpy-Cl)] + . [12] Thus, the three important bond angles in the central core of 1 (compare caption in Figure 1) agree very well with the reported corresponding ones for [Ir(ppy) 2 (k 2 N-terpy-Cl)] + : N6À Ir2À N7, 76.40 (15); N9À Ir2À C63, 80.19 (16) and N10À Ir2À C74, 81.12(18). [12] The IrÀ N and IrÀ C bond parameters within the cyclometalated chelating ring systems were in good accordance with the usually observed ones in related compounds reported by us.…”

“…The three bidentate chelating ligands complete a distorted octahedral coordination sphere around the central iridium atom. The coordination sphere of the cation in 1 is best comparable with that of the known complex [Ir(ppy) 2 (κ 2 N ‐terpy‐Cl)] + [12] . Thus, the three important bond angles in the central core of 1 (compare caption in Figure 1) agree very well with the reported corresponding ones for [Ir(ppy) 2 (κ 2 N ‐terpy‐Cl)] + : N6−Ir2−N7, 76.40(15); N9−Ir2−C63, 80.19(16) and N10−Ir2−C74, 81.12(18) [12] .…”

An infinite two-dimensional hybrid water–chloride network in a 4′-(furan-2-yl)-2,2′:6′,2′′-terpyridine nickel(II) matrix

“…4). Both the OÁ Á ÁO and OÁ Á ÁCl distances are comparable with those found in various types of water clusters and water-chloride associates (Safin et al, 2015;Bhat & Revankar, 2016;Ris et al, 2016). The resulting twodimensional network can be considered as a set of alternating cyclic fragments with three tetranuclear, three pentanuclear, one hexanuclear and two octanuclear fragments, as shown in Fig.…”

Redox cycling of iridium(III) complexes gives versatile materials for photonics applications

“…[1][2][3][4][5][6][7][8] Neutral compounds are required for OLEDs, whereas cationic [Ir(C^N)2(N^N)] + complexes with a neutral bidentate donor and two cyclometallated ligands are the commonest materials utilized in LECs. [1,2,8] Metal-binding domains within the C^N and N^N ligands include 2-phenylpyridine, 2-phenylpyrazole, [9] 2-thienylpyridine, [10] 2,2′:6′,2′′-terpyridine, [11,12] 1,10phenanthroline, [13] imidazole, [14] and triazole; [15] systematic variation allows tuning of the HOMO and LUMO energies and the related emission properties and device performances. However, the core structure remains cationic with the attendant materials properties (solubility in polar solvents, presence of an anion) which influence processability and device assembly and performance.…”