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em QUB Research Portal - Research Directory and Institutional Repository for Queen's University Belfast


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The metal-organic framework [Co(INA)(2)].0.5EtOH (INA = isonicotinate, NC5H4-4-CO2-), 1 was synthesised under solvothermal conditions. Its X-ray crystal structure shows channels containing ethanol guests which are hydrogen-bonded to carboxylate oxygens of the framework. The pyridyl rings of the framework alternate between `open' and `closed' positions along the channels resulting in large variation in the channel cross-sectional area from ca. 1.4 by 2.3 at the narrowest point to 4.9 by 5.3 at the widest. Despite the very small windows, the ethanol guests (of van der Waals diameter ca. 4.2-6.1 Angstrom) may be reversibly desorbed and sorbed into the structure quantitatively, as shown by in situ variable-temperture IR spectroscopy and XRPD. The single-crystal structure of the desolvated form [Co(INA)(2)]2 shows that there is no change in the overall connectivity on desolvation, but the rotational positions of the pyridine rings are altered. This suggests that pyridyl rotation may occur to allow guests to pass in and out. When the synthesis was conducted in 1-propanol solvent [Co(INA)(2)].0.5Pr(n)OH.H2O 3, was obtained, and a single-crystal X-ray structure revealed the same overall connectivity as in 1 but with pyridine rings disordered over closed and open positions. There was no evidence of included guests from X-ray crystallography, suggesting that they are also highly disordered. Variable-temperature XRPD performed on bulk samples showed peaks which were unsymmetrical and exhibited shoulders, suggesting that for each pattern obtained the material actually consisted of several closely-related phases. The movements of the peaks during desolvation showed the presence of intermediate phases before the final desolvated product was formed. The peak positions of the intermediate phases matched more closely with the calculated pattern for 3 than with 1 or 2, suggesting that they may have disordered structures similar to 3. The results also suggest that the intermediate phase represents an initial increase in volume before a larger decrease in volume occurs to give the final desolvated material.

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By 2015, with the proliferation of wireless multimedia applications and services (e.g., mobile TV, video on demand, online video repositories, immersive video interaction, peer to peer video streaming, and interactive video gaming), and any-time anywhere communication, the number of smartphones and tablets will exceed 6.5 billion as the most common web access devices. Data volumes in wireless multimedia data-intensive applications and mobile web services are projected to increase by a factor of 10 every five years, associated with a 20 percent increase in energy consumption, 80 percent of which is multimedia traffic related. In turn, multimedia energy consumption is rising at 16 percent per year, doubling every six years. It is estimated that energy costs alone account for as much as half of the annual operating expenditure. This has prompted concerted efforts by major operators to drastically reduce carbon emissions by up to 50 percent over the next 10 years. Clearly, there is an urgent need for new disruptive paradigms of green media to bridge the gap between wireless technologies and multimedia applications.

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The widespread availability and demand for multimedia capable devices and multimedia content have fueled the need for high-speed wireless connectivity beyond the capabilities of existing commercial standards. While fiber optic data transfer links can provide multigigabit- per-second data rates, cost and deployment are often prohibitive in many applications. Wireless links, on the contrary, can provide a cost-effective fiber alternative to interconnect the outlining areas beyond the reach of the fiber rollout. With this in mind, the ever increasing demand for multi-gigabit wireless applications, fiber segment replacement mobile backhauling and aggregation, and covering the last mile have posed enormous challenges for next generation wireless technologies. In particular, the unbalanced temporal and geographical variations of spectrum usage along with the rapid proliferation of bandwidth- hungry mobile applications, such as video streaming with high definition television (HDTV) and ultra-high definition video (UHDV), have inspired millimeter-wave (mmWave) communications as a promising technology to alleviate the pressure of scarce spectrum resources for fifth generation (5G) mobile broadband.

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