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ChemComm
Page 4 of 5
DOI: 10.1039/C8CC05402A
COMMUNICATION
Journal Name
Arpe, Industrial Organic Chemistry, Wiley-VCH, Weinheim,
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(a) S.-C. Xiang, Z. Zhang, C.-G. Zhao, K. Hong, X. Zhao, D.-R.
Ding, M.-H. Xie, C.-D. Wu, M. C. Das, R. Gill, K. M. Thomas
for CO2/N2 at 296 K, which is outstanding versus other MOFs
that are proficient in C2H2 sorption; this level of CO2/N2 selectiv-
ity is comparable to LIFM-26, which has a selectivity of 93.19
The Qst values obtained for C2H2, C2H4, C2H6, CO2 and CH4 in
PCM-48 help us to better understand the observed sorption se-
lectivity from a thermodynamic perspective (Figure 3D). The
values were obtained by fitting the 273 K and 296 K adsorption
isotherms of each gas to a virial-type equation, followed by the
calculation of Qst vales using the Clausius−Clapeyron equaꢀon.15
In order of increasing binding affinity, the calculated values
were: CH4, 11.4; CO2, 15.4; C2H4, 23.2; C2H6, 23.4; C2H2, 23.6 kJ
mol─1. All gases yielded sorption energies with positive slopes,
which is indicative of increasingly energetically-favourable host-
guest and guest-guest interactions, as more guest molecules be-
come adsorbed inside the microchannels.15 The Qst values ob-
tained for PCM-48 are within the normal range of magnitudes
observed previously for other MOFs.7-11,17-20 The measured Qst
value for CO2 is likely due to the presence of abundant polariz-
ing acetylenic and phosphine moieties inside the channels. Sim-
ilarly, the observed sorption preference for C2H2 is likely due to
a combination of this effect and enhanced acetylene polariza-
tion at the [Mn3(μ3-F)]5+ nodes. From an application standpoint,
Qst = 23.6 kJ mol─1 for C2H2 is well-suited for reversible C2H2
sorption, in that the desorption step would not incur a large en-
ergy penalty.
4
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In conclusion, we have demonstrated how a rationally-de-
signed MOF based on a novel acetylenic phosphine ligand was
able to preferentially adsorb C2H2 over related C1 and C2 gases
at room temperature. The inherent polarity of the microchan-
nels in PCM-48 also engendered high CO2 selectivity over N2,
also at room temperature. In future studies, we plan to utilize
the available phosphine lone pairs inside the PCM-48 channels
as sites to post-synthetically anchor low-valent metals as a
means to further tune the sorption selectivity.
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This work was supported by the National Science Foundation
under Grant No. DMR-1506694 and the Welch Foundation (F-
1738).
DOI:10.1002/anie.201802402; (d) He, N. W. Waggoner, S. G.
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Conflicts of interest
The authors declare no conflicts of interest.
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‡ Present address: State Key Laboratory of Silicon Materials, Cyrus
Tang Center for Sensor Materials and Applications, School of Ma-
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310027, China.
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