Synthesis, characterization and crystal structure determination of iron(III) hetero-ligand complexes containing 2,2′-bipyridine, 5,5′-dimethyl-2,2′-bipyridine and chloride, [Fe(bipy)Cl4][bipy·H] and [Fe(dmbipy)2Cl2][FeCl4]

A convenient synthesis of tris-heteroleptic polypyridyl [Ru(pp)(pp‘)(pp‘ ‘)]2+ complexes is reported (where pp, pp‘, and pp‘ ‘ represent three different polypyridyl ligands). Photolysis of [BzRu(pp)Cl]Cl (Bz = η6-C6H6) gives a mixture of Ru(pp)(CH3CN)2Cl2 and [Ru(pp)(CH3CN)3Cl]Cl. Refluxing this mixture with pp‘ yields Ru(pp)(pp‘)Cl2. Finally, refluxing Ru(pp)(pp‘)Cl2 with pp‘ ‘ in a 75% ethanol/water solution gives [Ru(pp)(pp‘)(pp‘ ‘)]2+. No ligand scrambling is observed. The complexes are characterized by 1H NMR, elemental analysis, FAB-MB, UV−vis and emission spectroscopy, and cyclic voltammetry.

Convenient synthesis of tris-heteroleptic ruthenium(II) polypyridyl complexes.

Three new platinum complexes containing 3,3‘-biisoquinoline (i-biq), [Pt(CN)2(i-biq)] (1), [PtCl2(i-biq)] (2), and [Pt(i-biq)2](PF6)2 (3), have been synthesized as orange-red, yellow, and colorless crystals, respectively. Their crystal structures and luminescence properties are reported. Crystal data:  for 1·0.5H2O, PtO0.5N4C20H13, orthorhombic, Pbcm, a = 13.989(2) A, b = 18.304(1) A, c = 6.682(3) A, V = 1710.9(6) A3, Z = 4, and final R = 0.039 (Rw = 0.033) for 970 independent reflections; for 2·DMF·H2O, PtCl2O2N3C21H21, triclinic, P1, a = 11.047(1) A, b = 12.397(3) A, c = 8.000(2) A, α = 106.56(1)°, β = 100.15(1)°, γ = 76.15(1)°, V = 1012.8(3) A3, Z = 2, and final R = 0.058 (Rw = 0.077) for 4219 independent reflections; for 3·2DMF, PtP2F12O2N6C42H38, triclinic, P1, a = 10.795(2) A, b = 13.511(2) A, c = 8.281(1) A, α = 105.22(1)°, β = 112.17(1)°, γ = 85.02(1)°, V = 1079.2(3) A3, Z = 1, and final R = 0.038 (Rw = 0.042) for 3606 independent reflections. Square-planar complexes of 1 are stacked in the crys...

Crystal Structures and Luminescence Properties of Platinum(II) Complexes Containing 3,3'-Biisoquinoline.

A series of chromophore−quencher complexes, trans-[Ru(bpy)2(pya)(pyb)]n+ (bpy = 2,2‘-bipyridyl; pya, pyb = substituted pyridyl ligands; n = 2−4) have been prepared and characterized. These contain combinations of the electron donor PTZ in py-PTZ (py-PTZ = 10-(4-picolyl)phenothiazine) and the electron acceptors MQ+ (1-methyl-4,4‘-bipyridinium cation), py-AQ (4-((((9,10-anthraquinon-2-yl)carbonyl)amino)methyl)pyridine), and py-MPAA (N-(4-pyridyl)-β-(1-methylpyridinium-3-yl)acrylamide cation), and 4-ethylpyridine (4-Etpy). The asymmetrical complexes (pya ≠ pyb) are synthesized by using the precursor trans-[Ru(bpy)2(DMSO)2](CF3SO3)2·0.5H2O, which is converted into trans-[Ru(bpy)2(py-PTZ)(DMSO)](CF3SO3)2·0.5H2O (1) by reaction with py-PTZ in DMSO/acetone at room temperature. 1 is treated with LiCl in aqueous DMF at 105 °C to prepare trans-[RuCl(bpy)2(py-PTZ)]CF3SO3·H2O (2). 2 is converted into the derivatives trans-[Ru(bpy)2(py-PTZ)(4-Etpy)](PF6)2·0.5H2O (5), trans-[Ru(bpy)2(py-PTZ)(MQ+)](PF6)3 (7), trans-[Ru(...

Trans-Chromophore-Quencher Complexes Based on Ruthenium(II)

The isocyanide ligand forms complexes with ruthenium(II) bis-bipyridine of the type [Ru(bpy)2(CNx)Cl](CF3SO3) (1), [Ru(bpy)2(CNx)(py)](PF6)2 (2), and [Ru(bpy)2(CNx)2](PF6)2 (3) (bpy = 2,2‘-bipyridi...

Synthesis, characterization, and photochemical and computational investigations of Ru(II) heterocyclic complexes containing 2,6-dimethylphenylisocyanide (CNx) ligand.

The cation trans -[Ru(bpy) 2 (PPh 3 ) 2 ] 2+ and trans -[Ru(Me 2 bpy 2 ) 2 (py) 2 ] 2+ both contain bipyridine ligands which are distorted because of the crowding of the two chelate units. The hexafluorophosphate salt of the first cation crystallizers in space group P2 1 /n, with a = 11.630(1), b = 20.245(2), c = 11.299(1)A, &#x03B2 = 103.99(1)°, and Z = 2. R = 0.047 for 2396 observed reflections. The hexafluorophosphate salt of the second cation crystallizers in space group C2/m, with a = 18.392(2), b = 11.265(1), c = 13.383(1)A, &#x03B2 = 139.42(2)°, and Z = 2. R = 0.047 for 1403 observed reflections. The Ru of the first cation lies on an inversion center and the Ru of the second cation lies on a special position of 2/m symmetry. The distortions of a number of bipyridine complexes with the trans geometry are analyzed and found to fall into two categories, bowed or twisted. The two complexes of this report were found to have a bowed conformation.

Structural Chemistry of Necessarily Distorted Bis(Bipyridine) Complexes. The Crystal Structure of the Trans-[Bis(2,2'-Bipyridine)Bis(Triphenul-Phosphine)Ruthenium(II)] and Trans-[Bis(4,4'-Dimethyl-2,2'-Bipyridine)Bis(Pyridine)Ruthenium(ii)] Cations

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Structural Chemistry of Necessarily Distorted Bis(Bipyridine) Complexes. The Crystal Structure of the Trans-[Bis(2,2'-Bipyridine)Bis(Triphenul-Phosphine)Ruthenium(II)] and Trans-[Bis(4,4'-Dimethyl-2,2'-Bipyridine)Bis(Pyridine)Ruthenium(ii)] Cations