10.1021/acs.chemmater.8b02511.s001
Yi Qi
Yi
Qi
Huoshu Xu
Huoshu
Xu
Xiaomin Li
Xiaomin
Li
Binbin Tu
Binbin
Tu
Qingqing Pang
Qingqing
Pang
Xiao Lin
Xiao
Lin
Erlong Ning
Erlong
Ning
Qiaowei Li
Qiaowei
Li
Structure Transformation of a Luminescent Pillared-Layer
Metal–Organic Framework Caused by Point Defects Accumulation
American Chemical Society
2018
luminescence property
coordination bond dissociations
Structure Transformation
XAS
framework
pillar ligands
bond dissociations
pore distribution
Raman spectroscopy
dipyridyl ligands
point defect formations
uncoordinated pyridyl group
pillared-layer MOF structure
FDM -22
metal sites
collapse
pyridine linkers
pyridyl group
X-ray absorption spectroscopy
zinc dicarboxylates
zinc metals
X-ray photoelectron spectroscopy
XPS
coordination bonds
2018-07-06 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Structure_Transformation_of_a_Luminescent_Pillared-Layer_Metal_Organic_Framework_Caused_by_Point_Defects_Accumulation/6843557
Pillared-layer
metal–organic frameworks (MOFs) are often
encountered to “collapse” upon external stimuli due
to weak interactions between the layers and the pillars. However,
the detailed local structural change, especially the accumulation
of defects due to intricately disordered bond dissociations, is not
clear due to the complicated and dynamic nature of the collapse. We
report a luminescent pillared-layer MOF structure, FDM-22, using zinc
dicarboxylates as layers and dipyridyl ligands as pillars, in which
three different transformed structures were captured along the increasing
number of coordination bond dissociations between zinc metals and
pyridine linkers. The transformation is triggered by these local point
defect formations in the MOF, which further contribute to the modulation
of its luminescence property, as well as prominent change in the morphology
and pore distribution of the MOF. Evidenced by Raman spectroscopy,
X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy
(XAS), each of the pillar ligands has only one pyridyl group coordinated
to a Zn(II) ion eventually, with the other uncoordinated pyridyl group
pointing to the pore. With ∼10% of the coordination bonds breaking
within the framework, FDM-22 provides a high concentration of active
metal sites in the framework.