Pore Modified FDU-12 as a Novel Container for Dendron Growth - The

Pore Modified FDU-12 as a Novel Container for Dendron Growth. Junxing Han†, Yueyun ... Publication Date (Web): September 20, 2017. Copyright © 2017...
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Pore Modified FDU-12 as a Novel Container for Dendron Growth Junxing Han, Yueyun Lou, Xiaoyang Cai, Bruce C Gibb, and Daniel Francis Shantz J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b05602 • Publication Date (Web): 20 Sep 2017 Downloaded from http://pubs.acs.org on September 28, 2017

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The Journal of Physical Chemistry

Pore Modified FDU-12 as a Novel Container for Dendron Growth Junxing Han§, Yueyun Lou§, Xiaoyang Cai‡, Bruce C. Gibb‡, and Daniel F. Shantz§,*

§

Department of Chemical and Biomolecular Engineering, Tulane University, 6823 St. Charles

Avenue, New Orleans, LA 70118, United States. Email: [email protected]



Department of Chemistry, Tulane University, 6823 St. Charles Avenue, New Orleans, LA

70118, United States.

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ABSTRACT.

The synthesis and characterization of a suite of melamine dendrons on FDU-12 and pore-expanded FDU-12 are reported. FDU-12, a mesoporous material with cubic arrays of pores possessing cage apertures of approximately 4 nm is not an efficient support for growing dendrons. However, pore-expanded FDU-12 (PE-FDU-12) is an effective support, and it is an efficient substrate for growing dendrons with high free volumes, i.e. bulkier spacer diamines, as compared to SBA-15. Extensive MALDI and solution NMR on the cleaved dendrons validate the other analytical methods used and confirm that the target fragments are formed. The findings from this work illustrate the effect of the silica support’s pore topology on the synthesis of dendron materials on solid supports.

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The Journal of Physical Chemistry

INTRODUCTION Organic – inorganic hybrid materials have attracted interest for a wide range of technological applications.1-7

In contrast to composite materials where one has macroscopic

domains of two different components, true hybrid materials have molecular or nanometer dispersion

of

the

two

components.

This

coupling

of

the

desirable

thermal/electrical/magnetic properties of an inorganic component with the chemical diversity of the organic component has led to hybrid materials to be of interest in fields as diverse as medicine,8-9 microelectronics,10 catalysis11 and separations.5, 12

Clearly this is a field that

will continue grow in both basic scientific research and real-world applications.4-5, 13 Since the initial reports of ordered mesoporous silica (OMS)

14-16

and the subsequent

grafting of organic functional groups onto OMS in the late 1990’s17-20 a large body of literature has developed investigating the attachment of simple functional groups onto OMS materials.20-21

Numerous studies have elucidated how the grafting conditions lead to

different spatial arrangements of functional groups.20-22

That work and material testing23

have shown that high surface area OMS with low (