TY - DATA T1 - Silver Cluster Formation, Dynamics, and Chemistry in Metal−Organic Frameworks PY - 2009/10/14 AU - Ronald J. T. Houk AU - Benjamin W. Jacobs AU - Farid El Gabaly AU - Noel N. Chang AU - A. Alec Talin AU - Dennis D. Graham AU - Stephen D. House AU - Ian M. Robertson AU - Mark D. Allendorf UR - https://acs.figshare.com/articles/media/Silver_Cluster_Formation_Dynamics_and_Chemistry_in_Metal_Organic_Frameworks/2821867 DO - 10.1021/nl901397k.s003 L4 - https://ndownloader.figshare.com/files/4519531 KW - uniform arrays KW - Ag 3 clusters KW - silver nanocluster formation KW - uniform pore sizes KW - particle sizes KW - metal nanoparticles KW - representative MOF templates KW - chemical stabilization KW - Silver Cluster Formation KW - MOF pores N2 - Synthetic methods used to produce metal nanoparticles typically lead to a distribution of particle sizes. In addition, creation of the smallest clusters, with sizes of a few to tens of atoms, remains very challenging. Nanoporous metal−organic frameworks (MOFs) are a promising solution to these problems, since their long-range crystalline order creates completely uniform pore sizes with the potential for both steric and chemical stabilization. We report a systematic investigation of silver nanocluster formation within MOFs using three representative MOF templates. The as-synthesized clusters are spectroscopically consistent with dimensions ≤1 nm, with a significant fraction existing as Ag3 clusters, as shown by electron paramagnetic resonance. Importantly, we show conclusively that very rapid TEM-induced MOF degradation leads to agglomeration and stable, easily imaged particles, explaining prior reports of particles larger than MOF pores. These results solve an important riddle concerning MOF-based templates and suggest that heterostructures composed of highly uniform arrays of nanoparticles within MOFs are feasible. ER -