?url_ver=Z39.88-2004&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Adc&rft.relation=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F38321%2F&rft.title=Rational+Control+of+Structure%2C+Composition%2C+and+Function+in+Metal-Organic+Frameworks&rft.creator=Muldoon%2C+Patrick&rft.description=This+dissertation+aims+to+address+several+challenges+in+the+chemistry+of+metal-organic+frameworks+(MOFs)+related+to+the+ability+to+precisely+incorporate+and+control+the+distribution+of+functional+components+throughout+these+unique+materials.+Herein+I+present+four+research+projects+which+span+from+controlling+the+composition+and+structural+topology+of+new+types+of+heterometallic+MOFs+to+developing+new+methods+for+the+systematic+modification+and+optimization+of+existing+materials+for+the+specific+applications+of+biological+imaging+and+carbon+capture.%0D%0AIn+Chapter+2+I+introduce+a+bottom-up+strategy+for+the+design+and+synthesis+of+new+MOFs+with+multiple+different+heterometallic+clusters%2C+achieving+systematic+and+differential+control+over+the+coordination+of+multiple+metals+during+the+assembly+of+these+frameworks.+Chapter+3+describes+a+unique+post+synthetic+strategy+for+optimizing+the+excitation+wavelengths+of+near+infrared+(NIR)+emitting+rare+earth+based+MOFs+for+biological+imaging.+This+approach+circumvents+the+need+for+large%2C+highly+delocalized+organic+chromophores+and+instead+relies+on+the+tight+packing+of+%CF%80-systems+formed+from+smaller+monomer+units+that+are+introduced+throughout+MOF+pores.+The+tight+packing+of+%CF%80-systems+results+in+long+wavelength+excitation%2Fabsorption+bands+that+are+a+synergistic+property+of+the+composite+material+not+observed+in+the+individual+organic+components+after+disassociation+of+the+MOFs.+Chapter+4+describes+the+combination+of+MOF-based+mixed-matrix+membrane+(MMM)+and+polymer+blending+approaches+to+form+exceptional+membranes+for+CO2%2FN2+separation.+Nano-sized+amino-functionalized+UiO-66+is+added+to+a+two-component+polymer+blend+to+create+a+series+of+MMMs+and+the+compatibility+of+the+component+parts+leads+to+property+enhancement%2C+in+particular+improved+gas+permeability%2C+mechanical+flexibility%2C+and+mitigated+physical+aging.+In+Chapter+5%2C+a+facile+method+for+independently+controlling+both+particle+size+and+surface+chemistry+of+UiO-66+through+ligand+exchange+is+demonstrated.+This+strategy+allows+for+a+wide+variety+of+functional+groups+to+be+installed+at+the+external+surface+of+nano-sized+MOF+particles+with+systematically+variable+densities+which+can+be+used+to+optimize+MOF+particles+for+various+applications.&rft.date=2020-06-08&rft.type=University+of+Pittsburgh+ETD&rft.type=PeerReviewed&rft.format=application%2Fpdf&rft.language=en&rft.identifier=http%3A%2F%2Fd-scholarship-dev.library.pitt.edu%2F38321%2F25%2FMuldoon_Thesis.pdf&rft.identifier=++Muldoon%2C+Patrick++(2020)+Rational+Control+of+Structure%2C+Composition%2C+and+Function+in+Metal-Organic+Frameworks.++Doctoral+Dissertation%2C+University+of+Pittsburgh.++++(Unpublished)++