A novel Pt(II) terpyridine complex that has a nicotinamide moiety linked to the terpyridyl ligand has been synthesized in good yield and studied structurally and spectroscopically. The complex, [Pt(Nttpy)Cl](PF(6))(2) where Nttpy = 4'-(p-nicotinamide-N-methylphenyl)-2,2':6',2' '-terpyridine, is observed to be brightly luminescent in the solid state at room temperature and at 77 K. The complex exhibits reversible vapochromic behavior and crystallographic change in the presence of several volatile organic solvents. Upon exposure to methanol vapors, the complex changes color from red to orange, and a shift to higher energy is observed in the emission maximum with an increase in excited-state lifetime and emission intensity. The crystal and molecular structures of the orange and red forms, determined by single-crystal X-ray diffraction on the same single crystal, were found to be equivalent in the molecular sense and only modestly different in terms of packing. In both forms, the cationic Pt(II) complexes possess distorted square planar geometries. Analysis of the orange form's crystal packing reveals the presence of solvent molecules in lattice voids, Pt...Pt separations averaging 3.75 A and a zigzag arrangement between nearest neighbor Pt atoms, whereas the red form is devoid of solvent within the crystal lattice and contains complexes stacked with a nearly linear arrangement of Pt(II) ions having an average distance of 3.33 A. On the basis of the crystallographic data, it is evident that sorption of methanol vapor induces a change in intermolecular contacts and Pt...Pt interactions in going from red to orange. Disruption of the d(8)-d(8) metallophilic interactions consequently alters the emitting state from (3)[(d)sigma*-pi*(terpyridine)] that is formally a metal-metal-to-ligand charge transfer (MMLCT) state in the red form to one in which the HOMO corresponds to a more localized Pt(d) orbital in the red form ((3)MLCT).

We report two new molecularly engineered push-pull dyes, i.e., YA421 and YA422, based on substituted quinoxaline as a π-conjugating linker and bulky-indoline moiety as donor and compared with reported IQ4 dye. Benefitting from increased steric hindrance with the introduction of bis(2,4-dihexyloxy)benzene substitution on the quinoxaline, the electron recombination between redox electrolyte and the TiO2 surface is reduced, especially in redox electrolyte employing Co(II/III) complexes as redox shuttles. It was found that the open circuit photovoltages of IQ4, YA421, and YA422 devices with cobalt-based electrolyte are higher than those with iodide/triiodide electrolyte by 34, 62, and 135 mV, respectively. Moreover, the cells employing graphene nanoplatelets on top of gold spattered film as a counter electrode (CE) show lower charge-transfer resistance compared to platinum as a CE. Consequently, YA422 devices deliver the best power conversion efficiency due to higher fill factor, reaching 10.65% at AM 1.5 simulated sunlight. Electrochemical impedance spectroscopy and transient absorption spectroscopy analysis were performed to understand the electrolyte influence on the device performances with different counter electrode materials and donor structures of donor-π-acceptor dyes. Laser flash photolysis experiments indicate that even though the dye regeneration of YA422 is slower than that of the other two dyes, the slower back electron transfer of YA422 contributes to the higher device performance.

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Recently, dye-sensitized solar cells (DSC) have attracted much attention with their low production costs of electricity and relatively high energy-conversion efficiencies. [1][2][3][4] One of the key elements in DSC is the nanoporous TiO 2 electrode, which transfers the electrons from the dye molecules to the transparent conductive-oxide (TCO) electrode and concurrently allows the electrolytes to diffuse to the anchored dyes. Typically, nanoparticles are utilized for the fabrication of the nanoporous TiO 2 layers on the TCO to obtain high surface areas and generate nanopored structures. [1,5,6] In this TiO 2 layer derived from nanoparticles, however, the electrons produced from the dye molecules have to pass through numerous grain boundaries in order to reach the TCO, and the transport of the electrolytes is not efficient due to the irregularity of the pores generated. To this point, the tailoring of TiO 2 nanostructures is a crucial aspect of increasing the current photovoltaic-conversion efficiency of DSC. [7][8][9][10][11][12][13][14][15][16][17][18][19] For the formation of an efficient DSC, a high surface area is prime and essential for the TiO 2 layer to load large amounts of dye molecules that will generate electrons by absorbing sun light. Second, the pores formed in the TiO 2 layer must be sufficiently large in size with excellent mutual connectivity for the efficient diffusion of electrolytes. Third, the defect level and the number of grain boundaries must be minimized to suppress the loss of electrons by recombination or back reaction. In general, however, these factors are not compatible with one another. For example, upon decreasing the size of the TiO 2 nanoparticles, the surface area of the fabricated nanoporous TiO 2 film is increased, and thus more dye molecules can be adsorbed. However, the average pore size is decreased simultaneously, and more defect sites and grain boundaries can be generated in the fabricated TiO 2 film. Therefore, it has been reported that the optimum particle size of TiO 2 has to be in the range of 12-20 nm. [5,6,[20][21][22] In this work, we designed a novel hierarchical pore structure that provides high surface area and large pore size at the same time. That is, nanoporous TiO 2 spheres with high surface area were synthesized and utilized to form the nanoporous TiO 2 electrode. As a result, two kinds of pores were successfully formed in the TiO 2 layer. Tiny internal pores were formed inside the TiO 2 sphere, while large external pores were generated by formation of the interstitial voids among the spherical structures. The large external pores can be used as a ''highway'' for electrolyte diffusion, as shown in Scheme 1. Therefore, it is expected that this porous spherical structure can provide both great adsorption of the dye molecules and efficient electrolyte diffusion at the same time.Sub-micrometer-sized TiO 2 spheres have often been prepared by sol-gel methods controlling the hydrolysis and condensation reactions, and their crystallized structures were formed by su...

A donor−chromophore−acceptor triad (D−C−A) in which the chromophore is a Pt diimine bis(acetylide) moiety (red), the donor is phenothiazine (blue), and the acceptor is nitrophenyl (green) has been synthesized and studied spectroscopically. Irradiation leads to a charge-separated state that has a 70 ns lifetime as measured by transient absorption spectroscopy.

Submicron-sized monodispersed TiO 2 spheres (SPs) with high porosity were synthesized by a controlled hydrolysis of titanium tetraisopropoxide (TTIP) and subsequent hydrothermal treatment at 230 C. By adjusting the ratio of TTIP to water (the r-factor) in the hydrolysis reaction, the diameters of SPs were selectively controlled to 260, 350, 450, 560, 800, and 980 nm. The prepared SPs in the pure anatase phase were highly porous structures with crystallite sizes of $15 nm and surface areas of 101-121 m 2 g À1 . The synthesized nanoporous SPs in different sizes were then applied as the lightscattering layer (LSL) of dye-sensitized solar cells (DSCs) for efficient utilization of solar spectrum, and the size-dependent light-scattering effects of those SPs were systematically investigated. The 450 nm sized SP (SP450) provided the highest light-scattering efficiency among those in the 260-800 nm range. Relatively higher efficiency is caused by the characteristic light-scattering effect based on its unique diameter and also by the photonic reflection effect originating from its size-uniformity and long-range ordering. As a result the photovoltaic conversion efficiency (h) of DSC was improved from 6.92 to 9.04% with introducing the nanoporous SP450 as LSL.

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