We reevaluate the absolute fluorescence and phosphorescence quantum yields of standard solutions by using a novel instrument developed for measuring the absolute emission quantum yields of solutions. The instrument consists of an integrating sphere equipped with a monochromatized Xe arc lamp as the light source and a multichannel spectrometer. By using a back-thinned CCD (BT-CCD) as the detector, the sensitivity for spectral detection in both the short and long wavelength regions is greatly improved compared with that of an optical detection system that uses a conventional photodetector. Using this instrument, we reevaluate the absolute fluorescence quantum yields (Phi(f)) of some commonly used fluorescence standard solutions by taking into account the effect of reabsorption/reemission. The value of Phi(f) for 5 x 10(-3) M quinine bisulfate in 1 N H(2)SO(4) is measured to be 0.52, which is in good agreement with the value (0.508) obtained by Melhuish by using a modified Vavilov method. In contrast, the value of Phi(f) for 1.0 x 10(-5) M quinine bisulfate in 1 N H(2)SO(4), which is one of the most commonly used standards in quantum yield measurements based on the relative method, is measured to be 0.60. This value is significantly larger than Melhuish's value (0.546), which was estimated by extrapolating the value of Phi(f) for 5 x 10(-3) M quinine bisulfate solution to infinite dilution using the self-quenching constant. The fluorescence quantum yield of 9,10-diphenylanthracene in cyclohexane is measured to be 0.97. This system can also be used to determine the phosphorescence quantum yields (Phi(p)) of metal complexes that emit phosphorescence in the near-infrared region: the values of Phi(p) for [Ru(bpy)(3)](2+) (bpy = 2,2'-bipyridine) are estimated to be 0.063 in water and 0.095 in acetonitrile under deaerated conditions at 298 K, while that in aerated water, which is frequently used as a luminescent reference in biological studies, is reevaluated to be 0.040.

We synthesized a new porous coordination polymer Cu[Cu(pdt)2], which shows relatively high electrical conductivity (6 x 10(-4) S cm(-1) at 300 K) by the introduction of electron donors and acceptors as building units. This compound is applicable as a porous electrode with high power density. In addition, this compound forms a triangular spin lattice and shows spin frustration.

In recent years the phenomenon of negative thermal expansion (NTE; that is, contraction upon warming) over a broad temperature range has been detected in a select group of materials [1] and attributed to mechanisms that include electronic and magnetic transitions [2] and transverse atomic and molecular vibrations. [1,[3][4][5][6][7][8] Among the vibrational systems, materials that have received particular attention include AM 2 O 8 , AM 2 O 7 , A 2 M 3 O 12 , and a number of zeolites, [3] which contain MÀOÀM' bridges that undergo transverse vibration to cause contraction of the M-M' distance, and a diverse family of metal cyanides, [4][5][6][7][8] which contain MÀCNÀM' bridges that show an analogous effect but with increased vibrational flexibility. The presence of a highly flexible diatomic linker in the cyanide phases leads to pronounced thermal expansion behavior, examples of which include the largest isotropic [4] and anisotropic [5] NTE reported to date. A common NTE mechanism proposed for both the oxide and cyanide systems is the coupling of these transverse vibrations into concerted low-energy lattice modes that involve the rotation and/or translation of undistorted metal-coordination polyhedra, known as rigid unit modes (RUMs).[9] With thermal population, these modes counteract the higherenergy longitudinal modes that cause bond-length expansion, thereby leading to bulk NTE behavior.Recently, NTE has also been proposed in a series of isoreticular metal-organic framework (IRMOF) materials following the detected thermal contraction of gas-sorbed samples of IRMOF-1.[10] Theoretical simulations [11] of these materials have suggested an NTE mechanism closely analogous to that of the metal cyanide phases, [6,7] involving the transverse vibration of linear organic linkers. Following a more general investigation of such materials, herein we present the NTE properties of [Cu 3 (btc) 2 ] (btc = 1,3,5-benzenetricarboxylate), a metal-organic framework that consists of dicopper tetracarboxylate "paddlewheels" and aromatic ring motifs.[12] Through crystallographic characterization we elucidate a structural mechanism that involves two unique components: transverse vibration of planar, rather than linear, linkers, and local molecular vibrations within the framework.The highly symmetric structure of [Cu 3 (btc) 2 ] can be conveniently considered as consisting of octahedral supramolecular cages that link through their vertices to form a three-dimensional cubic framework (Figure 1 inset). As the material readily binds atmospheric water and gases at the coordinatively unsaturated Cu sites, [13] samples for powder and single-crystal X-ray diffraction measurement were sealed under vacuum in glass capillaries following their thorough

In the fields of fluid dynamics, aeronautical engineering, environment engineering, and energy technology, it is critical to accurately measure the physical parameters of a material surface. [1] Optoelectronic devices have generally been employed as temperature and pressure sensors. [2] However, their sensing area is limited to a single point on a surface. There is a need to measure entire surfaces and obtain multidimensional data for mapping surfaces. There are high expectations that materials for surface measurements, such as temperature and pressure-sensitive dyes, will overcome this intrinsic limitation of optoelectronic devices.We seek to design temperature-sensitive dyes using luminescent lanthanide complexes. Lanthanide complexes exhibit characteristic luminescence with narrow emission bands (full width at half maximum, fwhm < 10 nm) and long emission lifetimes (> 1 ms), [3] which make them suitable for use in sensing devices. In 2003, Amao and co-workers reported the first temperature-sensitive dye that employed an Eu III complex in a polymer film. [4] Khalil et al. demonstrated the high performance of an Eu III complex for a temperature-sensitive paint (temperature sensitivity: 4.42 % 8C À1 ). [5] We have reported a Tb III complex, Tb(hfa) 3 -(H 2 O) 2 (hfa: hexafluoro acetylacetonato), that is suitable as a temperature-sensing probe since it exhibits effective energy back transfer (BEnT) from the emitting level of the Tb III ion to the excited triplet state of the hfa ligand. [6] Since BEnT depends on the energy barrier of the process, the emission intensity varies with temperature.To improve the thermosensing performance, it is necessary to develop a thermostable structure for high-temperature sensing and to implement a dual sensing unit for a high sensing ability. First, we focused on a lanthanide coordination polymer to produce a thermostable structure. Thermally stable coordination polymers and metal-organic frameworks have been widely studied. [7] Carlos and co-workers recently reported novel three-dimensional lanthanide-organic frameworks with 2,5-pyridinedicarboxylic acid. [8] Marchetti et al. developed thermostable Eu III coordination polymers with 4acyl-pyrazolone ligands. [9] Here, we consider that introducing Tb III ion and hfa ligands to coordination polymer frameworks will produce a Tb III coordination polymer that can be used as a temperature-sensing probe. The triplet state of hfa (22 000 cm À1 ) is very close to the emitting level of the Tb III ion (20 500 cm À1 ), resulting in effective EnT1 and BEnT and thus high-performance thermosensing dyes (Figure 1 a). We also selected low-vibrational frequency phosphane oxide [10] as the linking part in the Tb III coordination polymer because lanthanide complexes with high emission quantum yields composed of hfa and bidentate phosphane oxide ligands have been reported. [11] Second, we attempted to impart ratiometric temperature sensing by using luminescent Eu III and Tb III ions in the frameworks of the coordination polymer to realize a high th...