Effects of the reaction cavity on metastable optical excitation in ruthenium-sulfur dioxide complexes

We report photoexcited-state crystal structures for two new members of the [Ru(SO_2)(NH_3)_4X]Y family: 1:X=H2O, Y=(+/-)-camphorsulfonate_2; 2:X=isonicotinamide, Y=tosylate_2. The excited states are metastable at 100 K, with a photoconversion fraction of 11.1(7)% achieved in 1, and 22.1(10)% and 26.9(10)% at the two distinct sites in 2.We further show using solid-state density-functional-theory calculations that the excited-state geometries achieved are strongly influenced by the local crystal environment. This result is relevant to attempts to rationally design related photoexcitation systems for optical data-storage applications.Comment: 6 pages, 5 figure

Discovery of Black Dye Crystal Structure Polymorphs: Implications for Dye Conformational Variation in Dye-Sensitized Solar Cells

We present the discovery of a new crystal structure polymorph (<b>1</b>) and pseudopolymorph (<b>2</b>) of the Black Dye, one of the world’s leading dyes for dye-sensitized solar cells, DSSCs (10.4% device performance efficiency). This reveals that Black Dye molecules can adopt multiple low-energy conformers. This is significant since it challenges existing models of the Black Dye···TiO₂ adsorption process that renders a DSSC working electrode; these have assumed a single molecular conformation that refers to the previously reported Black Dye crystal structure (<b>3</b>). The marked structural differences observed between <b>1</b>, <b>2</b>, and <b>3</b> make the need for modeling multiple conformations more acute. Additionally, the ordered form of the Black Dye (<b>1</b>) provides a more appropriate depiction of its anionic structure, especially regarding its anchoring group and NCS bonding descriptions. The tendency toward NCS ligand isomerism, evidenced via the disordered form <b>2</b>, has consequences for electron injection and electron recombination in Black Dye embedded DSSC devices. Dyes <b>2</b> and <b>3</b> differ primarily by the absence or presence of a solvent of crystallization, respectively; solvent environment effects on the dye are thereby elucidated. This discovery of multiple Black Dye conformers from diffraction, with atomic-level definition, complements recently reported nanoscopic evidence for multiple dye conformations existing at a dye···TiO₂ interface, for a chemically similar DSSC dye; those results emanated from imaging and spectroscopy, but were unresolved at the submolecular level. Taken together, these findings lead to the general notion that multiple dye conformations should be explicitly considered when modeling dye···TiO₂ interfaces in DSSCs, at least for ruthenium-based dye complexes

Solvent Effects on the UV–vis Absorption and Emission of Optoelectronic Coumarins: a Comparison of Three Empirical Solvatochromic Models

Coumarins often function in the solution phase for a diverse range of optoelectronic applications. The associated solvent effects on the UV–vis absorption and/or fluorescence spectral shifts of coumarins need to be understood in order that their photochemistry can be controlled. To this end, three different empirical solvatochromic models are assessed against 13 coumarins. The two generalized solvent scales developed by Catalán and co-workers demonstrate comparable performance to the popular Taft–Kamlet solvatochromic comparison method. A combinatorial approach to determine the best-fit equations in all of the empirical models is applied; this involves both statistical best-fits and the physical validation of the resulting parameters, based on the molecular structures of solvents and solutes and their corresponding interactions. The findings of this approach are used to extract useful information about different aspects of solvent effects on the solvatochromism of coumarins

Discovery of Black Dye Crystal Structure Polymorphs: Implications for Dye Conformational Variation in Dye-Sensitized Solar Cells

We present the discovery of a new crystal structure polymorph (<b>1</b>) and pseudopolymorph (<b>2</b>) of the Black Dye, one of the world’s leading dyes for dye-sensitized solar cells, DSSCs (10.4% device performance efficiency). This reveals that Black Dye molecules can adopt multiple low-energy conformers. This is significant since it challenges existing models of the Black Dye···TiO₂ adsorption process that renders a DSSC working electrode; these have assumed a single molecular conformation that refers to the previously reported Black Dye crystal structure (<b>3</b>). The marked structural differences observed between <b>1</b>, <b>2</b>, and <b>3</b> make the need for modeling multiple conformations more acute. Additionally, the ordered form of the Black Dye (<b>1</b>) provides a more appropriate depiction of its anionic structure, especially regarding its anchoring group and NCS bonding descriptions. The tendency toward NCS ligand isomerism, evidenced via the disordered form <b>2</b>, has consequences for electron injection and electron recombination in Black Dye embedded DSSC devices. Dyes <b>2</b> and <b>3</b> differ primarily by the absence or presence of a solvent of crystallization, respectively; solvent environment effects on the dye are thereby elucidated. This discovery of multiple Black Dye conformers from diffraction, with atomic-level definition, complements recently reported nanoscopic evidence for multiple dye conformations existing at a dye···TiO₂ interface, for a chemically similar DSSC dye; those results emanated from imaging and spectroscopy, but were unresolved at the submolecular level. Taken together, these findings lead to the general notion that multiple dye conformations should be explicitly considered when modeling dye···TiO₂ interfaces in DSSCs, at least for ruthenium-based dye complexes

Ru–OSO Coordination Photogenerated at 100 K in Tetraammineaqua(sulfur dioxide)ruthenium(II) (±)-Camphorsulfonate

The photoinduced O-bound coordination mode in RuSO₂ complexes, previously observed only at 13 K, has been generated at 100 K in tetraammineaqua­(sulfur dioxide)­ruthenium­(II) (±)-camphorsulfonate. This coordination state, often denoted MS1, decays to the η²-bound MS2 state, with an estimated half-life of 3.4(8) h and a long-lived population of 2.9(4)% at 120 K

Ru–OSO Coordination Photogenerated at 100 K in Tetraammineaqua(sulfur dioxide)ruthenium(II) (±)-Camphorsulfonate

The photoinduced O-bound coordination mode in RuSO₂ complexes, previously observed only at 13 K, has been generated at 100 K in tetraammineaqua­(sulfur dioxide)­ruthenium­(II) (±)-camphorsulfonate. This coordination state, often denoted MS1, decays to the η²-bound MS2 state, with an estimated half-life of 3.4(8) h and a long-lived population of 2.9(4)% at 120 K

Data mining with molecular design rules identifies new class of dyes for dye-sensitised solar cells

A major deficit in suitable dyes is stifling progress in the dye-sensitised solar cell (DSC) industry. Materials discovery strategies have afforded numerous new dyes; yet, corresponding solution-based DSC device performance has little improved upon 11% efficiency, achieved using the N719 dye over two decades ago. Research on these dyes has nevertheless revealed relationships between the molecular structure of dyes and their associated DSC efficiency. Here, such structure-property relationships have been codified in the form of molecular dye design rules, which have been judiciously sequenced in an algorithm to enable large-scale data mining of dye structures with optimal DSC performance. This affords, for the first time, a DSC-specific dye-discovery strategy that predicts new classes of dyes from surveying a representative set of chemical space. A lead material from these predictions is experimentally validated, showing DSC efficiency that is comparable to many well-known organic dyes. This demonstrates the power of this approach

CCDC 997759: Experimental Crystal Structure Determination

Related Article: Jacqueline M. Cole, Kian Sing Low, Hiroaki Ozoe, Panagiota Stathi, Chitoshi Kitamura, Hiroyuki Kurata, Petra Rudolf, Takeshi Kawase|2014|Phys.Chem.Chem.Phys.(PCCP)|16|26684|doi:10.1039/C4CP02645D,An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

Material Profiling for Photocrystallography: Relating Single-Crystal Photophysical and Structural Properties of Luminescent Bis-Cyclometalated Iridium-Based Complexes

The photophysical properties of seven luminescent iridium complexes are characterized in their single-crystal form, and the photoactivity is related to their molecular structures. Specifically, solid-state optical emission spectra and associated lifetimes are determined from single crystals of iridium complexes containing three bidentate ligands: two variously substituted 2-phenylbenzothiazoles and either a 2,4-pentadione (acetylacetone) or 2-pyridinecarboxylic (picolinic) acid. All complexes studied exhibit emissive behavior in the solid-state which originates from ³π–π* and metal-to-ligand-charge-transfer (MLCT) electronic transitions; this is supported by density functional theory. Phosphorescence is observed in all cases with microsecond lifetimes, ranging from 0.30 to 2.4 μs at 298 K and 1.4–4.0 μs at 100 K. Structure–property relationships are established which are relevant to the potential solid-state application of this series of luminescent complexes as organic light emitting diodes (OLED) material components. In addition, these materials are assessed for their suitability to time-resolved pump–probe photocrystallography experiments, which will reveal their photoexcited state structure. Accordingly, the design process by which materials are selected and technical parameters are defined for a photocrystallography experiment is illustrated. This family of complexes presents a case study for this photocrystallography material profiling. Results show that the time-resolved photoexcited state structure, featuring the MLCT transition is, in principle at least, viable for two of these complexes

Material Profiling for Photocrystallography: Relating Single-Crystal Photophysical and Structural Properties of Luminescent Bis-Cyclometalated Iridium-Based Complexes

The photophysical properties of seven luminescent iridium complexes are characterized in their single-crystal form, and the photoactivity is related to their molecular structures. Specifically, solid-state optical emission spectra and associated lifetimes are determined from single crystals of iridium complexes containing three bidentate ligands: two variously substituted 2-phenylbenzothiazoles and either a 2,4-pentadione (acetylacetone) or 2-pyridinecarboxylic (picolinic) acid. All complexes studied exhibit emissive behavior in the solid-state which originates from ³π–π* and metal-to-ligand-charge-transfer (MLCT) electronic transitions; this is supported by density functional theory. Phosphorescence is observed in all cases with microsecond lifetimes, ranging from 0.30 to 2.4 μs at 298 K and 1.4–4.0 μs at 100 K. Structure–property relationships are established which are relevant to the potential solid-state application of this series of luminescent complexes as organic light emitting diodes (OLED) material components. In addition, these materials are assessed for their suitability to time-resolved pump–probe photocrystallography experiments, which will reveal their photoexcited state structure. Accordingly, the design process by which materials are selected and technical parameters are defined for a photocrystallography experiment is illustrated. This family of complexes presents a case study for this photocrystallography material profiling. Results show that the time-resolved photoexcited state structure, featuring the MLCT transition is, in principle at least, viable for two of these complexes