Ravi K. Arvapally

Rigidifying fluorescent linkers by metal-organic framework formation for fluorescence blue shift and quantum yield enhancement.

We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 ± 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal-organic frameworks.

Metal-organic frameworks with high stability have been pursued for many years due to the sustainability requirement for practical applications. However, researchers have had great difficulty synthesizing chemically ultra-stable, highly porous metal-organic frameworks in the form of crystalline solids, especially as single crystals. Here we present a kinetically tuned dimensional augmentation synthetic route for the preparation of highly crystalline and extremely robust metal-organic frameworks with a preserved metal cluster core. Through this versatile synthetic route, we obtain large single crystals of 34 different iron-containing metal-organic frameworks. Among them, PCN-250(Fe2Co) exhibits high volumetric uptake of hydrogen and methane, and is also stable in water and aqueous solutions with a wide range of pH values.

Water Cluster Confinement and Methane Adsorption in the Hydrophobic Cavities of a Fluorinated Metal–Organic Framework

Water cluster formation and methane adsorption within a hydrophobic porous metal organic framework is studied by in situ vibrational spectroscopy, adsorption isotherms, and first-principle DFT calculations (using vdW-DF). Specifically, the formation and stability of H2O clusters in the hydrophobic cavities of a fluorinated metal-organic framework (FMOF-1) is examined. Although the isotherms of water show no measurable uptake (see Yang et al. J. Am. Chem. Soc. 2011 , 133 , 18094 ), the large dipole of the water internal modes makes it possible to detect low water concentrations using IR spectroscopy in pores in the vicinity of the surface of the solid framework. The results indicate that, even in the low pressure regime (100 mTorr to 3 Torr), water molecules preferentially occupy the large cavities, in which hydrogen bonding and wall hydrophobicity foster water cluster formation. We identify the formation of pentameric water clusters at pressures lower than 3 Torr and larger clusters beyond that pressure. The binding energy of the water species to the walls is negligible, as suggested by DFT computational findings and corroborated by IR absorption data. Consequently, intermolecular hydrogen bonding dominates, enhancing water cluster stability as the size of the cluster increases. The formation of water clusters with negligible perturbation from the host may allow a quantitative comparison with experimental environmental studies on larger clusters that are in low concentrations in the atmosphere. The stability of the water clusters was studied as a function of pressure reduction and in the presence of methane gas. Methane adsorption isotherms for activated FMOF-1 attained volumetric adsorption capacities ranging from 67 V(STP)/V at 288 K and 31 bar to 133 V(STP)/V at 173 K and 5 bar, with an isosteric heat of adsorption of ca. 14 kJ/mol in the high temperature range (288-318 K). Overall, the experimental and computational data suggest high preferential uptake for methane gas relative to water vapor within FMOF-1 pores with ease of desorption and high framework stability under operative temperature and moisture conditions.

Erratum: Corrigendum: Kinetically tuned dimensional augmentation as a versatile synthetic route towards robust metal–organic frameworks

Nature Communications 5: Article number: 5723 (2014); Published: 4 December 2014; Updated: 5 February 2015 The financial support for this Article was not fully acknowledged. The Acknowledgements should have read: This work was supported as part of the Methane Opportunities for Vehicular Energy (MOVE) Program under the Award Number DE-AR0000249 and as part of the Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center (EFRC) funded by the U.

Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air

The trinuclear triangle-shaped system [tris{3,5-bis(heptafluoropropyl)-1,2,4-triazolatosilver(I)}] (1) and the multi-armed square-shaped metalloporphyrin PtOEP or the free porphyrin base H2OEP serve as excellent octopus hosts (OEP=2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine). Coupling of the fluorous/organic molecular octopi 1 and H2OEP or PtOEP by strong quadrupole-quadrupole and metal-π interactions affords the supramolecular assemblies [1⋅PtOEP] or [1⋅H2OEP] (2 a), which feature nanoscopic cavities surrounding the upper triangular and lower square cores. The fluorous/organic biphasic configuration of [1⋅PtOEP] leads to an increase in the phosphorescence of PtOEP under ambient conditions. Guest molecules can be included in the biphasic double-octopus assembly in three different site-selective modes.

CCDC 975820: Experimental Crystal Structure Determination

Related Article: Dawei Feng, Kecheng Wang, Zhangwen Wei, Ying-Pin Chen, Cory M. Simon, Ravi Arvapally, Richard L. Martin, Mathieu Bosch, Tian-Fu Liu, Stephen Fordham, Daqiang Yuan, Mohammad A. Omary, Maciej Haranczyk, Berend Smit, Hong-Cai Zhou|2014|Nat.Commun.|5|5723|doi:10.1038/ncomms6723

Multi-Faceted Scientific Strategies Toward Better Solid-State Lighting of Phosphorescent OLEDs

This project has advanced solid-state lighting (SSL) by utilizing new phosphorescent systems for use in organic light-emitting diodes (OLEDs). The technical approach was two-fold: a) Targeted synthesis and screening of emitters designed to exhibit phosphorescence with maximized brightness in the solid state; and b) Construction and optimizing the performance of monochromatic and white OLEDs from the best new emitters to improve performance metrics versus the state of the art. The phosphorescent systems were screened candidates among a large variety of recentlysynthesized and newly-designed molecular and macromolecular metal-organic phosphors. The emitters and devices have been optimized to maximize light emission and color metrics, improve the long-term durability of emitters and devices, and reduce the manufacturing cost both by simplifying the process flow and by seeking less expensive device components than common ones. The project succeeded in all these goals upon comparison of the best materials and devices investigated vs. the state of the art of the technology.