TY - JOUR
T1 - Post-Synthetic Annealing
T2 - Linker Self-Exchange in UiO-66 and Its Effect on Polymer-Metal Organic Framework Interaction
AU - Smith, Stefan J. D.
AU - Konstas, Kristina
AU - Lau, Cher Hon
AU - Gozukara, Yesim Meltem
AU - Easton, Christopher D.
AU - Mulder, Roger J
AU - Ladewig, Bradley P.
AU - Hill, Matthew R.
AU - Hill, Matthew R.
PY - 2017/8/2
Y1 - 2017/8/2
N2 - Post-synthetic exchange (PSE) and defect engineering have emerged as powerful techniques for tuning the properties and introducing novel functionality to metal organic frameworks (MOFs). Growing evidence suggests that each technique plays a key role in the mechanism of the other: linker coordination chemistry is pivotal to defective frameworks, while defect sites can help initiate PSE. Here, the intersection of these approaches is explored by exchanging an MOF with linkers already present within the framework. Post-synthetic annealing (PSA) modifies an MOF's properties by redistributing the framework's mixture of bound linker/modulator species. Using changes to the polymer-additive interactions in poly-1-trimethylsilyl-1-propyne nanocomposites observed through aging, we demonstrate that PSA causes one linker species to preferentially accumulate on the MOF's crystal surface. Reaction conditions are shown to affect molecular composition of the resulting annealed UiO-66 MOFs, a finding explained through established reaction constants. This work simultaneously reveals intricacies of post-synthetic modification chemistry and presents a facile means of tuning MOFs and MOF nanocomposites.
AB - Post-synthetic exchange (PSE) and defect engineering have emerged as powerful techniques for tuning the properties and introducing novel functionality to metal organic frameworks (MOFs). Growing evidence suggests that each technique plays a key role in the mechanism of the other: linker coordination chemistry is pivotal to defective frameworks, while defect sites can help initiate PSE. Here, the intersection of these approaches is explored by exchanging an MOF with linkers already present within the framework. Post-synthetic annealing (PSA) modifies an MOF's properties by redistributing the framework's mixture of bound linker/modulator species. Using changes to the polymer-additive interactions in poly-1-trimethylsilyl-1-propyne nanocomposites observed through aging, we demonstrate that PSA causes one linker species to preferentially accumulate on the MOF's crystal surface. Reaction conditions are shown to affect molecular composition of the resulting annealed UiO-66 MOFs, a finding explained through established reaction constants. This work simultaneously reveals intricacies of post-synthetic modification chemistry and presents a facile means of tuning MOFs and MOF nanocomposites.
UR - http://www.scopus.com/inward/record.url?scp=85026865871&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.7b00685
DO - 10.1021/acs.cgd.7b00685
M3 - Article
AN - SCOPUS:85026865871
VL - 17
SP - 4384
EP - 4392
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 8
ER -