Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

New high technology product development: The case of light emitting diodes

New high technology products usher in novel possibilities to transform the design, production and use of buildings. The high technology companies which design, develop and introduce these new products by generating and applying novel scientific and technical knowledge are faced with significant market uncertainty, technological uncertainty and competitive volatility. These characteristics present unique innovation challenges compared to low- and medium technology companies. This paper reports on an ongoing Construction Knowledge Exchange funded project which is tracking, real time, the new product development process of a new family of light emitting diode (LEDs) technologies. LEDs offer significant functional and environmental performance improvements over incumbent tungsten and halogen lamps. Hitherto, the use of energy efficient, low maintenance LEDs has been constrained by technical limitations. Rapid improvements in basic science and technology mean that for the first time LEDs can provide realistic general and accent lighting solutions. Interim results will be presented on the complex, emergent new high technology product development processes which are being revealed by the integrated supply chain of a LED module manufacture, a luminaire (light fitting) manufacture and end user involved in the project.

Radiometric analysis of the light coupled by optimally cut plastic optical fiber amplitude modulating reflectance displacement sensors

A radiometric analysis of the light coupled by optical fiber amplitude modulating extrinsic-type reflectance displacement sensors is presented. Uncut fiber sensors show the largest range but a smaller responsivity. Single cut fiber sensors exhibit an improvement in responsivity at the expense of range. A further increase in responsivity as well as a reduction in the operational range is obtained when the double cut sensor configuration is implemented. The double cut configuration is particularly suitable in applications where feedback action is applied to the moving reflector surface. © 2000 American Institute of Physics.

Evaluation of dichroic material for enhancing light pipe/natural ventilation and daylighting in an integrated system

Integration of natural ventilation and daylighting in a single installation would make both technologies more attractive. One method for the integration is the use of concentric light pipe and ventilation stack. By constructing the light pipe using dichroic materials, the infrared part of the solar radiation is allowed to be transmitted to the stack but the visible light is guided by the light pipe into a room. The heat gain to the interior can be reduced and the thermal stack effect strengthened. Work presented here involved the experimental and computational evaluation of dichroic materials for enhancing both natural stack ventilation and daylighting. The transmittance of a dichroic light pipe was found to be similar to that of a light pipe with a 95% specular reflectance. The infra-red radiation transmitted through the dichroic material into a passive stack was found to enhance the natural ventilation flow by up to 14%. The effect is greater in summer than in winter, which is highly desirable as there is often a lack of driving force for natural stack ventilation in summer.

Solar physics: shining a light on solar impacts

Comparing changes in temperature and solar radiation on centennial timescales can help to constrain the Sun’s impact on climate. New findings regarding the minimum activity level of the Sun reveal that comparisons made so far may have been too simplistic.