Ru complexes of thienyl-functionalized dipyrrins as NCS-free sensitizers for the dye-sensitized solar cell.

We report the first case of Ru(II) dipyrrinates employed as dyes in dye-sensitized solar cells. These complexes exhibit panchromatic light harvesting that results in significant DSSC current densities, rendering them promising for photovoltaic applications. Adjustment of the lowest excited state energy is required to boost the power conversion efficiency.

Cycloruthenated sensitizers: improving the dye-sensitized solar cell with classical inorganic chemistry principles.

A divergence from the conventional approach to chromophore design has led to the establishment of many exciting new benchmarks for the dye-sensitized solar cell (DSSC), including the first documented power conversion efficiency in excess of 12% at 1 sun illumination [Yella et al., Science 2011, 334, 629]. Paramount to these advances is the deviation from polypyridyl ruthenium dyes bearing NCS(-) ligands, such as [Ru(dcbpy)(2)(NCS)(2)] (N3; dcbpy = 4,4'-dicarboxy-2,2'-bipyridine).

Three is not a crowd: efficient sensitization of TiO2 by a bulky trichromic trisheteroleptic cycloruthenated dye.

A cyclometalated Ru dye bearing two triphenylamine groups to augment light absorption exhibits a power conversion efficiency (PCE) in excess of 7% in the dye-sensitized solar cell despite having a large molecular footprint on TiO(2).

External-stimuli responsive photophysics and liquid crystal properties of self-assembled "phosphole-lipids".

A series of new amphiphilic phosphonium materials that combine the electronic features of phospholes with self-assembly features of lipids were synthesized. Variable concentration/temperature and 2D NMR studies suggested that the systems undergo intramolecular conformation changes between a "closed" and "open" form that are triggered by intermolecular interactions. The amphiphilic features of the phospholium species also induce liquid crystalline and soft crystal phase behavior in the solid state, which was studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and variable temperature powder X-ray diffraction (VT-PXRD).

Cyclometalated Ru complexes of type [Ru(II)(N--N)(2)(C--N)](z): physicochemical response to substituents installed on the anionic ligand.

The electrochemical and photophysical properties of a series of Ru(II) complexes related to [Ru(dcbpyH(2))(2)(ppy)](1+) (1; dcbpyH(2) = 4,4'-dicarboxy-2,2'-bipyridine; ppy = 2-phenylpyridine) were examined to elucidate the effect of modifying the anionic fragment of the C--N ligand with conjugated substituents (R). Included in this study is a family of compounds (2-5) consisting of one or two -NO(2) groups installed meta, ortho, and para to the organometallic bond. A suite of compounds with electron-donating and withdrawing groups (e.

On the viability of cyclometalated Ru(II) complexes for light-harvesting applications.

The effects of replacing a single polypyridyl ligand with an analogous anionic cyclometalating ligand were investigated for a set of three structurally related series of Ru(II) compounds formulated as [Ru(bpy)(2)(L)](z), [Ru(tpy)(L)](z), and [Ru(tpy)(L)Cl](z), where z = 0, +1, or +2, and L = polypyridyl (e.g., bpy = 2,2'-bipyridine, tpy = 2,2':6',2''-terpyridine) or cyclometalating ligand (e.

A convenient preparative method for cyclic triphosphenium bromide and chloride salts.

Analytically pure chloride and bromide salts of two different cyclic triphosphenium cations are prepared by the reaction of PX3 (X=Cl, Br) in the presence of the halogen-scavenging reagent cyclohexene. For the brominated species, the neutral, volatile 1,2-dibromocyclohexane byproduct is readily removed under reduced pressure, and the desired salts are obtained in high yield. Reactions involving phosphorus trichloride are complicated by the formation of salts containing both chloride and hydrogen dichloride anions.