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Review
. 2014 Apr 22;19(4):5028-87.
doi: 10.3390/molecules19045028.

RutheniumII complexes bearing fused polycyclic ligands: from fundamental aspects to potential applications

Ludovic Troian-Gautier  1 , Cécile Moucheron  2
Affiliations
Review

RutheniumII complexes bearing fused polycyclic ligands: from fundamental aspects to potential applications

Ludovic Troian-Gautier et al. Molecules. .

Abstract

In this review, we first discuss the photophysics reported in the literature for mononuclear ruthenium complexes bearing ligands with extended aromaticity such as dipyrido[3,2-a:2',3'-c]phenazine (DPPZ), tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]-phenazine (TPPHZ), tetrapyrido[3,2-a:2',3'-c:3'',2''-h:2''',3'''-j]acridine (TPAC), 1,10-phenanthrolino[5,6-b]1,4,5,8,9,12-hexaazatriphenylene (PHEHAT) 9,11,20,22-tetraaza- tetrapyrido[3,2-a:2',3'-c:3'',2''-l:2''',3'''-n]pentacene (TATPP), etc. Photophysical properties of binuclear and polynuclear complexes based on these extended ligands are then reported. We finally develop the use of binuclear complexes with extended π-systems for applications such as photocatalysis.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
[Ru(bpy)3]2+.
Figure 2
Figure 2
Photophysical scheme of [Ru(bpy)3]2+.
Figure 3
Figure 3
[Ru(phen)2(DPPZ)]2+ (left) and [Ru(bpy)2(DPPZ)]2+ (right).
Figure 4
Figure 4
Schematic representation of the luminescence lifetime with temperature for [Ru(bpy)3]2+ and [Ru(bpy)2(DPPZ)]2+ [97].
Figure 5
Figure 5
Photophysical scheme of [Ru(bpy/phen)2(DPPZ)]2+ in water.
Figure 6
Figure 6
Solvent influence on the dark and bright states.
Figure 7
Figure 7
Schematic relaxation pathway for [Ru(phen)2(DPPZ)]2+ in polyol solvents [100].
Figure 8
Figure 8
The seven DPPZ derivatives reported by Barton [11].
Figure 9
Figure 9
[Ru(bpy)2(dmDPPZ)]2+.
Figure 10
Figure 10
[Ru(bpy)2(dppp2)]2+ (left) and [Ru(bpy)2(dpqp)]2+ (right).
Figure 11
Figure 11
Jablonski diagrams of [Ru(bpy)2(dppp2)]2+ in CH2Cl2 (left), CH3CN (center), and CH3CH2OH (right). MLCTdist stands for the distal portion of DPPZ while MLCTprox stands for the proximal portion of DPPZ [112].
Figure 12
Figure 12
[Ru(TAP)2(DPPZ)]2+.
Figure 13
Figure 13
Tridentate ligands used in the studies performed by Turro.
Figure 14
Figure 14
RutheniumII complexes bearing a pydppn ligand (left) or a pydppz ligand (right).
Figure 15
Figure 15
3-(Pyrid-2'-yl)-4,5,9,16-triazadibenzo[a,c]naphthacene (pyHdbn).
Figure 16
Figure 16
Jablonski diagrams for various ruthenium complexes [118].
Figure 17
Figure 17
RutheniumII complexes bearing dppn, bpy and ppy ligands.
Figure 18
Figure 18
Relative energies of the low-lying triplet states of rutheniumII complexes bearing dppn, bpy and ppy ligands [119].
Figure 19
Figure 19
Examples of ligands with extended π-systems.
Figure 20
Figure 20
[Ru(tbbpy)2(TPPHZ)]2+ with bromine substituted TPPHZ.
Figure 21
Figure 21
[Ru(bpy)2(dmTPPHZ)]2+.
Figure 22
Figure 22
[Ru(phen)2(TPAC)]2+.
Figure 23
Figure 23
[Ru(phen)2(HAT)]2+.
Figure 24
Figure 24
[Ru(phen)2(PHEHAT)]2+ (left) and [Ru(phen)2(HATPHE)]2+ (right).
Figure 25
Figure 25
Photophysical scheme for [Ru(phen)2(PHEHAT)]2+.
Figure 26
Figure 26
Binuclear TPPHZ complexes.
Figure 27
Figure 27
Photophysical mechanism for the RuII-RuII TPPHZ binuclear complex in CH2Cl2 (left) and CH3CN (right) [155].
Figure 28
Figure 28
Photophysical mechanism for the OsII-OsII TPPHZ binuclear complex in CH2Cl2 (left) and CH3CN (right) [155].
Figure 29
Figure 29
Schematic picture of the charge distribution along the photophysical pathway for the RuII-OsII TPPHZ binuclear complex in CH2Cl2 (blue) and CH3CN (red) [155].
Figure 30
Figure 30
Photophysical mechanism for the RuII-OsIII TPPHZ binuclear complex in CH3CN [155].
Figure 31
Figure 31
{[Ru(bpy)2]2(HAT)}4+.
Figure 32
Figure 32
The complexes [Ru(phen)2(PHEHAT)Ru(phen)2]4+ (left) and [Ru(phen)2(PHEHAT)Ru(bpy)2]4+ (right).
Figure 33
Figure 33
The complexes [Ru(TAP)2(PHEHAT)Ru(phen)2]4+ (left) and [Ru(phen)2(PHEHAT)Ru(TAP)2]4+ (right).
Figure 34
Figure 34
[Ru(phen)2(TAPC)Ru(phen)2]4+ (left) and [Ru(TAP)2(TPAC)Ru(TAP)2]4+ (right).
Figure 35
Figure 35
The two binuclear complexes, [Ru(phen)2(tatpp)Ru(phen)2]4+ and [Os(phen)2(tatpp)Os(phen)2]4+.
Figure 36
Figure 36
Energy level of the 3MLCT and 3LC states for the homodinuclear RuII-tatpp complex [161].
Figure 37
Figure 37
Energy level of the 3MLCT and 3LC states for the homodinuclear OsII-tatpp complex [161].
Figure 38
Figure 38
Relative energy of the 3MLCT and 3LC states of the RuII and OsII complexes based on TPPHZ and tatpp [161].
Figure 39
Figure 39
Schematic representation of the energy transfer in polynuclear complexes bearing 2,3-dpp bridging ligands [163,165].
Figure 40
Figure 40
A Ruthenium dendrimer containing twenty-two metal centers [167].
Figure 41
Figure 41
Pathway for the synthesis of the heptanuclear RuII core dendrimer [168].
Figure 42
Figure 42
Pathway for the synthesis of the first ligand-cored nonanuclear dendrimer [171].
Figure 43
Figure 43
{Ru[PHEHAT-Ru(phen)2]3}8+ (left) and {Ru[PHEHAT-Ru(bpy)2]3}8+ (right).
Figure 44
Figure 44
Schematic representation of the oxidation and reduction processes in PHEHAT and TPPHZ tetranuclear complexes.
Figure 45
Figure 45
Schematic representation of a dinuclear subunit present in the dendritic compound.
Figure 46
Figure 46
Complexes used by Vos [139].
Figure 47
Figure 47
Charge distribution along the photophysical pathway for [Ru(tbbpy)2(TPPHZ)]2+ [206].
Figure 48
Figure 48
Charge distribution along the photophysical pathway for [Ru(tbbpy)2(TPPHZ)PdCl2]2+ [206].
Figure 49
Figure 49
[Ru(tbbpy)2(TPPHZ)]2+ bearing a bromine substituted TPPHZ.
Figure 50
Figure 50
RutheniumII complex with various extended π-systems.
Figure 51
Figure 51
{[(Ru(tbbpy)2)2(µ-PHAT)]PdCl2}4+.
Figure 52
Figure 52
The trinuclear complex based on tatpp [Pd{(tatpp)Ru(phen)2}2]6+.
Figure 53
Figure 53
[Ru(bpy)2(bqpy)Ru(bpy)2]4+.
Scheme 1
Scheme 1
Redox pathway for [Ru(bpy)2(bqpy)Ru(bpy)2]4+.
Figure 54
Figure 54
Representation of the related redox and protonation isomers for [Ru(phen)2(tatpq)Ru(phen)2]4+.
Figure 55
Figure 55
Electron and proton transfer processes in water at pH 11 (red), 8.5 (blue) and 6 (pink) [216].
Figure 56
Figure 56
Qualitative molecular orbital energy diagram for the redox and protonation isomers of [Ru(phen)2(tatpp)Ru(phen)2]4+ [215].
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