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Title: Pillar[5]arene Based Conjugated Microporous Polymers for Propane/Methane Separation through Host–Guest Complexation

Authors:
 [1];  [1];  [2];  [1];  [1];  [3]
  1. Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea
  2. Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States
  3. Graduate School of Energy, Environment, Water and Sustainability (EEWS), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea; Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388675
DOE Contract Number:
SC0001015
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 28; Journal Issue: 12; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University
Country of Publication:
United States
Language:
English
Subject:
membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Talapaneni, Siddulu Naidu, Kim, Daeok, Barin, Gokhan, Buyukcakir, Onur, Je, Sang Hyun, and Coskun, Ali. Pillar[5]arene Based Conjugated Microporous Polymers for Propane/Methane Separation through Host–Guest Complexation. United States: N. p., 2016. Web. doi:10.1021/acs.chemmater.6b01667.
Talapaneni, Siddulu Naidu, Kim, Daeok, Barin, Gokhan, Buyukcakir, Onur, Je, Sang Hyun, & Coskun, Ali. Pillar[5]arene Based Conjugated Microporous Polymers for Propane/Methane Separation through Host–Guest Complexation. United States. doi:10.1021/acs.chemmater.6b01667.
Talapaneni, Siddulu Naidu, Kim, Daeok, Barin, Gokhan, Buyukcakir, Onur, Je, Sang Hyun, and Coskun, Ali. 2016. "Pillar[5]arene Based Conjugated Microporous Polymers for Propane/Methane Separation through Host–Guest Complexation". United States. doi:10.1021/acs.chemmater.6b01667.
@article{osti_1388675,
title = {Pillar[5]arene Based Conjugated Microporous Polymers for Propane/Methane Separation through Host–Guest Complexation},
author = {Talapaneni, Siddulu Naidu and Kim, Daeok and Barin, Gokhan and Buyukcakir, Onur and Je, Sang Hyun and Coskun, Ali},
abstractNote = {},
doi = {10.1021/acs.chemmater.6b01667},
journal = {Chemistry of Materials},
number = 12,
volume = 28,
place = {United States},
year = 2016,
month = 6
}
  • Phosphoryl (P=O), urea (N/sub 2/C=O), pyridine, and pyridine oxide (N ..-->.. O) groups have been incorporated into the ring systems of macrocyclic polyethers. The association constants of the resulting eight new ligand systems toward Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/, and NH/sub 4//sup +/ picrates in CHCl/sub 3/ were surveyed, and the free energies of association were estimated. The P=O complexing sites were covalently bonded through two attached o-tolyl groups as in the unit RP(O)(C/sub 6/H/sub 4/CH/sub 2/-o)/sub 2/, in which different R groups were attached to phosphorus. The resulting unit, written as RPOD, was attachedmore » to two ether oxygens (0), which in turn were connected through CH/sub 2/CH/sub 2/ or E units to form macrocycles. Ligand systems C/sub 6/H/sub 5/POD(OEOE)/sub 2/O (9), C/sub 6/H/sub 5/POD(OEOEO)/sub 2/E (10), o-HO/sub 2/CC/sub 6/H/sub 4/POD(OEOE)/sub 2/O (11), o-CH/sub 3/O/sub 2/CC/sub 6/H/sub 4/POD(OEOE)/sub 2/O (12), CH/sub 3/OPOD(OEOE)/sub 2/O (13), and C/sub 6/H/sub 5/POD(OEO)/sub 2/PODC/sub 6/H/sub 5/ (14 and 15, the syn and anti isomers) were synthesized and examined. The urea complexing site was cyclic, CH/sub 2/(CH/sub 2/N)/sub 2/C = O (abbreviated to UON), and was bonded through its two nitrogens to E units. The cycle prepared and examined was UON(EOEOE)/sub 2/O (16). The pyridine and pyridine oxide complexing sites were bonded through CH/sub 2/ groups in their ..cap alpha..,..cap alpha..' positions to comprise the units ..cap alpha..-CH/sub 2/(C/sub 5/H/sub 3/N)CH/sub 2/-..cap alpha.. and ..cap alpha..-CH/sub 2/(C/sub 5/H/sub 3/NO)CH/sub 2/-..cap alpha.., respectively, the latter of which was abbreviated as POM. The new cycle prepared and examined was POM(OEOE)/sub 2/O (18). The patterns of ..delta..G/sup 0/ values of complexation of these ligand systems were compared to those of 2,3-naphtho 18-crown-6 (19), 2,6-pyrido-18-crown-6 (20), and 1,3-benzo-18-crown-5 (21). The results suggest that those ligand systems whose organization of binding sites before and after complexation are the most similar show the highest structural recognition toward the anions.« less
  • The association constants (K/sub a/, M/sup -1/) and free energies of binding (-..delta..G/sup 0/), kcal mol/sup -1/) have been measured at 25 /sup 0/C in CDCl/sub 3/ saturated with D/sub 2/O for cryptahemispherands, cryptands, and diazahemispherand binding the alkali metal picrate salts. Methods were used in which complexes whose K/sub a/ values had been determined were equilibrated with hosts of unknown values. The equilibrium points were determined by /sup 1/H NMR spectral methods. The cryptahemispherands as a class were found to be more powerful complexing agents than the cryptands. The two classes exhibited comparable ion selectivities. Plots of the -..delta..G/supmore » 0/ values of the cryptands in CDCl/sub 3/-D/sub 2/O vs. those in 95% CH/sub 3/OH-5% H/sub 2/O were linear. The -..delta..G/sup 0/ values for eight different sets of binding partners in CDCl/sub 3/-D/sub 2/O were found to be 5.2 +/- 0.4 kcal mol/sup -1/ higher than the corresponding eight values in CH/sub 3/OH-H/sub 2/O. The results are discussed in terms of the relative states of preorganization for binding and desolvation of the various host classes.« less
  • The synthesis and chromogenic properties of 1 as a sodium and lithium ion selective indicator system are described. The pK/sub a/ values of 1 in the absence and presence of various metal ions were measured in 80% dioxane-20% water (v/v). Observed values were as follows: Li/sup +/, 5.9; Na/sup +/, 6.9; K/sup +/, 12.7; Ca/sup 2 +/, 12.8; Mg/sup 2 +/, 13.2; 1,5-diazabicyclo(4.3.0)non-5-ene (DBN), 13.0. The noncomplexing model system 21 gave a pK/sub a/ of 10.8 in the same medium. Spherand 1 is yellow (lambda/sub max/ 396 nm; epsilon/sub max/ 17,500 L/(mol x cm)), whereas spheraplexes 1/sup -/ x Li/supmore » +/ (lambda/sub max/ 586 nm, epsilon/sub max/ 35,500 L/(mol X cm)), and 1/sup -/ x Na/sup +/ (lambda/sub max/ 596 nm, epsilon/sub max/ 35,500 L/(mol x cm)) as well as uncomplexed 1/sup -/ (lambda/sub max/ 610 nm, epsilon/sub max/ 53,000 L/(mol x cm)) are deep blue or violet in 80% dioxane-20% water (v/v) and other solvents. Thus 1 is a chromogenic ion-selective indicating system capable of detecting Li/sup +/ and Na/sup +/ at concentrations as low as 10/sup -8/ M in the presence of other common ions. The binding free energies of spherands 4-6 binding lithium picrate and sodium picrate at 25/sup 0/C in CDCl/sub 3/ saturated with D/sub 2/O were measured and found to range between 8.4 and 12.5 kcal mol/sup -1/, somewhat higher than those for 7, but much lower than those for 2.« less
  • Syntheses and crystal structures are reported for a new class of hosts, their complexes, and their precursors. The cryptahemispherands are composed of molecular modules that are half spherand and half cryptand. They were synthesized by the reactions of diacid chloride and cyclic diamines to produce diamides, reduction of which gave the desired hosts. Cryptahemispherands form a variety of complexes with the alkali metal cations. Crystal structures were determined for the isomeric diamides for the hydroborane complex, and for alkali cation complexes.
  • Syntheses are reported for 16 new macrocyclic polyether ligand systems which contain potentially convergent side chains containing additional binding sites. The free energies of association of these systems in CDCl/sub 3/ at 25/sup 0/C with Li/sup +/, Na/sup +/, K/sup +/, Rb/sup +/, Cs/sup +/, NH/sub 4//sup +/, CH/sub 3/NH/sub 3//sup +/, and t-BuNH/sub 3//sup +/ picrates were determined.