Earlier studies of phosphine-substituted terthiophenes have demonstrated that some of these materials exhibit nonlinear absorption at 532 nm. However, this wavelength is significantly removed from the linear absorption maxima of the complexes, suggesting that better nonlinear absorption might be observed at wavelengths closer to the linear absorption maxima. To investigate this possibility, a library of compounds has been prepared either by varying the group attached to the nonbonding pair of electrons on the phosphorus atoms of 5,5''-bis(diphenylphosphino)-2,2':5',2''-terthiophene (PT(3)P), or by introducing additional substituents on the 5''-position of 5-(diphenylphosphino)-2,2':5',2''-terthiophene (PT(3)). All these compounds have been characterized using multinuclear NMR, UV-vis, and fluorescence spectroscopy. The compounds are strongly fluorescent, and both the fluorescence wavelength and the intensity depend upon the thiophene substituents. The nonlinear optical properties have also been evaluated at various wavelengths in the blue region. Each compound exhibits reverse saturable absorption, and the intensity of the reverse saturable absorption at a particular wavelength depends on the chemical structure of the compound.
Perylenediimide functionalized bridged siloxane nanoparticles were prepared by direct hydrolysis and condensation of a perylenediimide silane precursor in the presence of a catalytic amount of tetraethoxysilane (TEOS). The sizes of the particles were controlled by adjusting organotrialkoxysilane, base, and TEOS concentrations. Using this modified Stöber method, we were able to incorporate a higher load of organic content (∼70%) into the siloxane core compared to typical organically modified Stöber silica nanoparticles. The size, shape, and surface morphology of these functionalized particles were visualized using transmission electron microscopy. Their compositions were confirmed by FTIR, thermogravimetric analysis, and elemental analysis. The photovoltaic performance of these nanohybrids in the poly(3-hexylthiophene) polymer matrix was evaluated. The device made from a sample annealed at 150 °C showed reasonably good photovoltaic performance with a power conversion efficiency of 1.56% under standard test conditions of AM 1.5G spectra at an illumination intensity of 100 mW cm(-2).
b S Supporting Information T he physical chemistry laboratory course is an essential experience to the student wishing to pursue an advanced degree in chemistry or a career in a chemistry related field. A study in 2004 on physical chemistry curriculum points out that physical chemistry bridges physics, chemistry, and mathematics and develops complex critical-thinking skills required by scientists working on projects with interdisciplinary foci. 1 Physical chemistry now encompasses subareas too numerous to list and contributes to the study of almost all the other disciplines in chemistry. Today in a growing number of universities, however, the physical chemistry lab has been scaled back from the traditional two-semester period to just one semester. For example, in a recent informal survey of chemistry programs in the Southern Universities Group, approximately a quarter of the schools now only require one semester of physical chemistry lab to obtain a B.S. degree in chemistry. The loss of a whole semester has different roots, such as the desire to reduce the number of hours in a major or to make room for other new specialty courses such as environmental or forensic chemistry. The problem, therefore, arises in being able to provide students with enough lab experience to encompass the important areas of physical chemistry. Moore pointed out that it is extremely important to make sure the physical chemistry curriculum reflects what physical chemists really do. 2 With this in mind, in 1999, the University of Maryland integrated a program of physical and analytical techniques to investigate significantly more complex systems than those incorporated with one curriculum. 3 In 2004, Grand Valley State University sought to incorporate both computational and traditional physical chemistry laboratories in their curriculum, stating that the coupling of laboratories allows students to experience an experiment from a macroscopic, empirical point of view as well as an abstract, theoretical level that considers molecular-level events. 4 Combining multiple laboratory procedures into fewer multidimensional lab exercises allows students to be provided with opportunities encompassing multiple facets of physical chemistry in a constrained time frame. 5 Constructing a binary liquidÀvapor phase diagram is a classic physical chemistry experiment that is still taught in many chemistry departments and serves to illustrate an important physical concept. Here, we show that two other important concepts can be taught concurrently in this laboratory exercise, specifically molecular spectroscopy and quantum chemistry.The classic binary liquidÀvapor phase diagram experiment utilizes Raoult's law, which states that vapor pressure of an ideal solution is directly proportional to the mole fraction of each component. This law is a good approximation for a component only when its mole fraction is close to unity. Deviations, positive or negative, from Raoult's law give insight into the thermodynamic properties of the components involved. There have been...
Poly(3-hexylthiophene)-functionalized siloxane nanoparticles were prepared by a modified Stöber method. The photovoltaic performance of P3HT-nanohybrids with C60 derivative PCBM was evaluated. The device made from 1 : 1 blends of P3HT-NPs:PCBM showed reasonably good photovoltaic performance with a power conversion efficiency of 2.5% under standard test conditions (AM 1.5G, 100 mW cm(-2)).
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