Magnetic field [kOe] Temperature [K] Pore width [nm]

1 Functional Metal Organic Frameworks: Chemistry and Applications Darpandeep Aulakh,1 Joshua Pyser,1 Xuan Zhang,2 Juby Varghese,1 Andrey Yakovenko,3 Kim Dunbar2 and Mario Wriedt1. 1 Department of Chemistry & Biomolecular Science, Clarkson University, Potsdam, NY 13699. 2 Department of Chemistry, Texas A&M University, College Station, TX 77845. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439. MOFs as Platforms for the Controlled Nanostructuring of Single Molecule Magnets The materials currently used for data storage are rapidly approaching their limits (meaning we will no longer be able to store more information in increasingly smaller spaces with the current technologies).

2 1 Therefore, new and smaller materials are in high demand. Nanomagnets, such as single molecule magnets (SMM), are an intriguing solution to this problem as they could potentially increase data storage capacities thousands of times. CH3CN. However, these materials are delicate and need to be contained in a type of nanostructure +. Room temp in order to make them possibly viable for data Metal-organic frameworks 12 hr (MOFs), with their well defined multi-dimensional cavities can act as excellent hosts for these nanomagnets. Loading the nanomagnets into the pores of the MOF would allow for Mn12Ac the individual molecules to be separated from one another, as well as providing protection for them.

3 Hopefully, this technique can eventually be used to produce a macroscopic material with the intent to increase data storage capacities. CYCU-3 Synthesis of SMM@MOF composite Powder X-Ray Diffraction Analysis Adsorption Analysis 1200 100. Physical mixture [ : ; 2 : 1]. = Observed Cumulative pore volume [cm3g-1]. Differential pore volume [cm3g-1]. Calculated MOF (2) MOF (2). Relative intensity [ ]. 1000. Quantity adsorbed [cm3g-1]. Difference 80 Mn12Ac@MOF (3) MOF (2). Bragg position Mn12Ac@MOF (3). Mn12Ac@MOF (3) 800 Total volume in pores: Intensity [ ]. 60. Mn12Ac@MOF (3) Mn12Ac@MOF (3) cm3g-1 (2).

4 600 cm3g-1 (3) 40. (200). (300). (210). (100). (420). (410). (310). (400). Mn12Ac (1). 400 BET surface areas: m2g-1 (2) 20. MOF (2) CYCU-3 (2) m2g-1 (3). 200. 0. 0. 1 2 3 4 5 6 6 8 10 12 14 16 18 20 2-Theta [deg] 2-Theta [deg] p/p0 Pore width [nm] Pore width [nm]. Synchrotron PXRD data Difference Envelope Experimental N2 Adsorption Isotherm Pore Size Distribution Cumulative Pore Volume Density Magnetic Properties Analysis Conclusions 6 Successful insertion of SMM Mn12Ac into a mesoporous host K 1 Hz T = K. K 10 Hz 4. K 100 Hz Sufficiently large pore size and relatively unreactive interior of framework Magnetization [ ].

5 K 1 kHz 2. facilitate insertion and preservation of SMM's unique Magnetic properties '' [emu mol-1]. '' [emu mol-1]. K kHz K. K 0. K K. K -2 Only a single SMM cluster is loaded in transverse direction of pores, K. K. -4. yielding a long range ordered crystalline composite material while showing K. significantly enhanced thermal stability -6. 1 10 100 1000 2 3 4 5 6 7 8 9 10 -15 -10 -5 0 5 10 15. Wave frequency [Hz] Temperature [K]. Magnetic field [kOe]. These findings will pave way for new venues for development of novel Frequency Dependence Temperature Dependence Magnetic field Hysteresis advanced high density information storage devices of Magnetic AC Susceptibility of Magnetic AC Susceptibility Photofunctional Zwitterionic MOFs with Tunable Adsorption Properties quartz capillary gas in X-rays uv source with sample gas out Stimuli responsive adsorption behavior Photochromic behavior heating/cooling Diffraction This set up will be used at 17-BM for in-situ investigation of MOFs exhibiting photochromic behavior

6 References Acknowledgement 1. Sanvito et al., Chem. Soc. Rev. 2011, 40, 3336 Use of the Advanced Photon Source was supported 2. Bogani et al., Nat Mater 2008, 7, 179 by the U. S. Department of Energy, Office of Science, 3. Woodruff et al., Chem. Rev. 2013, 113, 5110 Office of Basic Energy Sciences, under contract no. 4. Domingo et al., Chem. Soc. Rev. 2012, 41, 258 DE-AC02-06CH11357.