Recently, porous organic cage crystals have become a real alternative to extended framework materials with high specific surface areas in the desolvated state. Although major progress in this area has been made, the resulting porous compounds are restricted to the microporous regime, owing to the relatively small molecular sizes of the cages, or the collapse of larger structures upon desolvation. Herein, we present the synthesis of a shape-persistent cage compound by the reversible formation of 24 boronic ester units of 12 triptycene tetraol molecules and 8 triboronic acid molecules. The cage compound bears a cavity of a minimum inner diameter of 2.6 nm and a maximum inner diameter of 3.1 nm, as determined by single-crystal X-ray analysis. The porous molecular crystals could be activated for gas sorption by removing enclathrated solvent molecules, resulting in a mesoporous material with a very high specific surface area of 3758 m(2)  g(-1) and a pore diameter of 2.3 nm, as measured by nitrogen gas sorption.

When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.

The relationship between the structure and the properties of a drug or material is a key concept of chemistry. Knowledge of the three-dimensional structure is considered to be of such...

The complexes [Cu(I)(POP)(dmbpy)][BF4] (1) and [Cu(I)(POP)(tmbpy)][BF4] (2) (dmbpy = 4,4'-dimethyl-2,2'-bipyridyl; tmbpy = 4,4',6,6'-tetramethyl-2,2'-bipyridyl; POP = bis[2-(diphenylphosphino)-phenyl]ether) have been studied in a wide temperature range by steady-state and time-resolved emission spectroscopy in fluid solution, frozen solution, and as solid powders. Emission quantum yields of up to 74% were observed for 2 in a rigid matrix (powder), substantially higher than for 1 of around 9% under the same conditions. Importantly, it was found that the emission of 2 at ambient temperature represents a thermally activated delayed fluorescence (TADF) which renders the compound to be a good candidate for singlet harvesting in OLEDs. The role of steric constraints within the complexes, in particular their influences on the emission quantum yields, were investigated by hybrid-DFT calculations for the excited triplet state of 1 and 2 while manipulating the torsion angle between the bipyridyl and POP ligands. Both complexes showed similar flexibility within a ±10° range of the torsion angle; however, 2 appeared limited to this range, whereas 1 could be further twisted with little energy demand. It is concluded that a restricted flexibility leads to a reduction of nonradiative deactivation and thus an increase of emission quantum yield.

Unlike their transition-metal analogues, the oxo groups of the uranyl dication, [UO 2 ] 2+ , which has a linear geometry and short, strong UÀO bonds are commonly considered inert. [1] Very little Lewis base character has been demonstrated for the uranyl oxo groups, [2,3] which makes them poor models for the heavier, highly radioactive transuranic actinyl cations such as neptunyl [NpO 2 ] n+ (n = 1, 2). [4,5] The heavier actinyls are important components in nuclear waste and demonstrate oxo basicity that can give rise to poorly understood cluster formation and problems in nuclear waste PUREX separation processes.[6] However, it has been shown recently that the more Lewis basic, pentavalent uranyl cation, [UO 2 ] + , can be stabilized indefinitely using suitable equatorial-binding ligands and anaerobic conditions. [7,8] Usually the [UO 2 ] + cation decomposes by disproportionation, which is also a poorly understood process, but is important in the precipitation of uranium salts out of aqueous environments. [9,10] The disproportionation is suggested, by analogy with the transuranic metal oxo Lewis base behavior, to involve the formation of cation-cation interactions (CCIs) [11,12] in which the oxo groups ligate to adjacent actinyl centers forming diamond (A) or T-shaped (B) dimers or clusters which can then allow the transfer of protons and electrons between metals, such as in C. [13] We reported that the use of rigid, Pacman-shaped macrocycles can allow the isolation of heterobimetallic uranyltransition metal complexes that form an oxo interaction with the transition metal in the solid state and solution, [14] and how the inclusion of more than one metal cation alongside the uranyl cation led to isolable, stable pentavalent uranyl complexes with a covalently functionalized oxo group. [15] More recently, pentavalent uranyl complexes with Group 1 cation oxo-coordination, [16] and a doubly silylated complex [17] have been isolated. Here, we report the first uranyl-4f metal interaction, prepared by either standard, or sterically induced reduction procedures, and demonstrate strong magnetic coupling between the 4f and 5f electrons.The reaction between the divalent samarium silylamide [Sm(THF) 2 {N(SiMe 3 ) 2 } 2 ] and the uranyl Pacman complex [UO 2 (py)(H 2 L)] (1) in pyridine resulted in the deposition of the new uranyl-samarium complex [UO 2 Sm(py) 2 (L)] 2 (2) as a very poorly soluble, thermally stable, red crystalline powder in good yield (Scheme 1), and containing crystals suitable for single-crystal X-ray diffraction studies (Figure 1).The 1 H NMR spectrum of 2 in [D 5 ]pyridine reveals the presence of paramagnetically shifted resonances between d = 12.4 and À21.5 ppm, the number and integrals of which are consistent with the retention of a wedged, Pacman structure in solution of C s symmetry. In the solid state, the molecular structure shows that 2 is dimeric (Figure 1) and the unit cell contains two similar molecules. Focusing on one molecule of 2, both the uranium and samarium centers are sevencoordinate w...