Soumya Mukherjee | University of Limerick (original) (raw)

Papers by Soumya Mukherjee

Research paper thumbnail of Crystal engineered hybrid ultramicroporous materials for single-step ethylene purification from C2–CO2 ternary mixture

Acta Crystallographica Section A Foundations and Advances

Mankind is now in the "age of gas"[1] and there are urgent needs in gas purification that will li... more Mankind is now in the "age of gas"[1] and there are urgent needs in gas purification that will likely only be solved by a new generation of physisorbent porous materials that offer reduced cost and superior performance. Engaging the principles of crystal engineering, hybrid ultramicroporous materials, HUMs (pore size < 0.7 nm) [2], by means of combining small pores (< 0.7 nm) with strong electrostatics offer an ideal sorbent platform suited for tight-fit of the target sorbate, resulting in performance benchmarks over the recent years [3, 4]. However, due to narrow pore networks imposing steric restrictions, crystal engineering of modular HUMs on account of organic ligand functionalisation has remained largely elusive. Moving one step ahead of the synergistic sorbent separation technology [5], herein we address single-step purification of ethylene (C 2 H 4), the highest volume product of the chemical industry, by crystal engineering of two HUMs of formula [Ni(pyz-NH 2) 2 (MF 6)] n (pyz-NH 2 = aminopyrazine, 17; M = Si, Ti), MFSIX-17-Ni [6]. Isostructural pyrazine analogues (SIFSIX-3-Zn [7], SIFSIX-3-Ni [8]) are the benchmark physisorbents for trace carbon capture but are unsuited for acetylene capture. No single physisorbent has the requisite selectivity to purify C 2 H 4 from ternary C 2-CO 2 mixtures (C 2 H 4 /C 2 H 2 /CO 2) under ambient conditions until now. Indeed, both MFSIX-17-Ni sorbents produce polymer grade ethylene (> 99.95% purity) from a 1:1:1 ternary mixture (Figure 1). Regarding insights for the future, we attribute the observed properties to the unusual binding sites in MFSIX-17-Ni that offer comparable affinity to both CO 2 and C 2 H 2 , thereby enabling coadsorption of C 2 H 2 and CO 2. In situ synchrotron x-ray diffraction, in situ IR spectroscopy and molecular modelling provide insight into these binding sites and why they differ from those of the pyrazine-linked materials. Figure 1. Schematic illustration of MFSIX-17-Ni that exhibits single-step C 2 H 4 purification by simulatneous CO 2 and C 2 H 2 removal.

Research paper thumbnail of Amino‐Functionalised Hybrid Ultramicroporous Materials that Enable Single‐Step Ethylene Purification from a Ternary Mixture

Angewandte Chemie International Edition, 2021

Pyrazine-linked hybrid ultramicroporous (pore size < 7)m aterials (HUMs) offer benchmark performa... more Pyrazine-linked hybrid ultramicroporous (pore size < 7)m aterials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO 2 over small gas molecules,i ncluding light hydrocarbons.T hat the prototypal pyrazine-linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX-3-Zn, mainly through substitution of the metal and/or the inorganic pillar.Herein, we report that two isostructural aminopyrazinelinked HUMs, MFSIX-17-Ni (17 = aminopyrazine;M = Si, Ti), whichwehad anticipated would offer even stronger affinity for CO 2 than their pyrazine analogs,u nexpectedly exhibit reduced CO 2 affinity but enhanced C 2 H 2 affinity. MFSIX-17-Ni are consequently the first physisorbents that enable singlestep production of polymer-grade ethylene (> 99.95 %f or SIFSIX-17-Ni)from aternary equimolar mixture of ethylene, acetylene and CO 2 thanks to coadsorption of the latter two gases.W ea ttribute this performance to the very different binding sites in MFSIX-17-Ni versus SIFSIX-3-Zn.

Research paper thumbnail of Spiers Memorial Lecture: Coordination networks that switch between nonporous and porous structures: an emerging class of soft porous crystals

Faraday Discussions, 2021

This review of soft coordination networks that undergo guest-induced switching between nonporous ... more This review of soft coordination networks that undergo guest-induced switching between nonporous and porous structures addresses switching mechanisms and their potential utility.

Research paper thumbnail of Trace CO 2 capture by an ultramicroporous physisorbent with low water affinity

Science Advances, 2019

The first sorbent with high CO 2 selectivity and poor water affinity addresses need for trace CO ... more The first sorbent with high CO 2 selectivity and poor water affinity addresses need for trace CO 2 remediation in confined spaces.

Research paper thumbnail of Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution

Angewandte Chemie, 2019

Coordination networks that reversibly switch between closed and open phases are of topical intere... more Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacity for gas storage applications than related rigid porous coordination networks. In order to be of practical utility, the pressures at which switching occurs, the gate-opening and gate-closing pressures. Here we study the effect of linker substitution to fine-tune gate-opening and gate-closing pressure. Specifically, three variants of a previously reported pcu topology MOF, X-pcu-5-Zn, have been prepared. X-pcu-6-Zn, 6 = 1,2-bis(4pyridyl)ethane (bpe), X-pcu-7-Zn, 7 = 1,2-bis(4-pyridyl)acetylene (bpa) and X-pcu-8-Zn, 8 = 4,4'-azopyridine (apy), each exhibited switching isotherms but at different gate-opening pressures. The N2, CO2, C2H2 and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gateopening and gate-closing pressures. This simple design principle enables rational control of the switching behaviour in adsorbent materials.

Research paper thumbnail of Hydrophobic metal-organic frameworks: Potential toward emerging applications

APL Materials, 2019

Barrier materials for flexible bioelectronic implants with chronic stability-Current approaches a... more Barrier materials for flexible bioelectronic implants with chronic stability-Current approaches and future directions APL Materials 7, 050902 (2019);

Research paper thumbnail of Stabilizing Metal–Organic Polyhedra (MOP): Issues and Strategies

Chemistry – An Asian Journal, 2019

Research paper thumbnail of Crystal engineering of dichromate pillared hybrid ultramicroporous materials incorporating pyrazole-based ligands

CrystEngComm, 2018

Short and sterically encumbered pyrazole ligands have led to the first examples of non-interpenet... more Short and sterically encumbered pyrazole ligands have led to the first examples of non-interpenetrated, dichromate pillared hybrid ultramicroporous materials.

Research paper thumbnail of Coordination Network That Reversibly Switches between Two Nonporous Polymorphs and a High Surface Area Porous Phase

Journal of the American Chemical Society, 2018

We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn 2 (DMTDC) 2 (dpe... more We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn 2 (DMTDC) 2 (dpe)] (H 2 DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene), that exhibits reversible switching between an as-synthesized "open" phase, X-pcu-5-Zn-, and two nonporous or "closed" polymorphs, X-pcu-5-Zn- and X-pcu-5-Zn-. There are two unusual features of X-pcu-5-Zn. The first relates to its sorption properties, which reveal that the  form Scheme 1. Structural transformations of X-pcu-5-Zn.

Research paper thumbnail of Recyclable switching between nonporous and porous phases of a square lattice (sql) topology coordination network

Chemical communications (Cambridge, England), Jan 21, 2018

A nonporous square lattice (sql) coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits ... more A nonporous square lattice (sql) coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits recyclable switching induced by CO2. The sorption isotherms are stepped with moderate hysteresis, temperature controlled and saturation uptake is fixed. Such switching, which has rarely been observed, offers the promise of exceptional working capacity for gas storage.

Research paper thumbnail of Self-assembled, Fluorine-rich Porous Organic Polymers: A Class of Mechanically Stiff and Hydrophobic Materials

Chemistry (Weinheim an der Bergstrasse, Germany), Jan 29, 2018

Fluorous organic building blocks have been cogently harnessed to develop two self-assembled, hydr... more Fluorous organic building blocks have been cogently harnessed to develop two self-assembled, hydrophobic and fluorinated porous organic polymers (FPOPs) namely, FPOP-100 and FPOP-101. On comprehensive mechanical analyses of these functionalized triazine network polymers, they mark the introduction of mechanical stiffness among all porous organic network materials; recorded stiffness features analogous to their organic-inorganic hybrid polymer analogues, viz. metal-organic frameworks (MOFs). Further, the study presents a new paradigm for the simultaneous installation of mechanical stiffness and high surface hydrophobicity into polymeric organic networks, which has the utilitarian potential to be translated among all porous solids. Control experiments with non-fluorinated congeners could underline the key role of fluorine, in particular, bis(trifluoromethyl)-functionalization behind realizing the dual features of mechanical stiffness and superhydrophobicity.

Research paper thumbnail of Polar Pore Surface Guided Selective CO2 Adsorption in a Prefunctionalized Metal–Organic Framework

Crystal Growth & Design, 2017

Selective CO 2 adsorption over other small gases has been realized in an ultramicroporous metal-o... more Selective CO 2 adsorption over other small gases has been realized in an ultramicroporous metal-organic framework (MOF). In the quest of manifesting such selective carbon capture performance, the pre-functionalized linker strategy has been espoused. A new Zn(II)-based three-dimensional, threefold interpenetrated MOF material [Zn(PBDA)(DPNI)] n .xG (PBDA: 4,4'-((2-(tert-butyl)-1,4-phenylene)bis(oxy))dibenzoic acid; DPNI: N,N'-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide; xG: x number of guest species) with unusual rob topology is synthesized following a typical solvothermal synthesis protocol, which gleans a modest CO 2-selective adsorption trend over its congener gases (saturation CO 2 uptake capacity: 2.39 and 3.44 mmolg-1 , at 298K and 273K; volumetric single component isotherm based separation ratios at 0.2 bar: 189.4 (CO 2 /N 2 , 256.5 (CO 2 /H 2), 12.3 (CO 2 /CH 4); at 1 bar: 6.8 (CO 2 /N 2 , 17.1 (CO 2 /H 2), 7.1 (CO 2 /CH 4)). The compound also exhibits selective benzene sorption over its aliphatic C 6-analogue cyclohexane. The structure-property correlation guided results supported by theoretical introspection further emphasize the omnipresent role of crystal engineering principles behind culmination of such targeted properties in the nanoporous MOF domain, to realize selective sorption facets.

Research paper thumbnail of Chiral Biomolecule Based Dodecanuclear Dysprosium(III)-Copper(II) Clusters: Structural Analyses and Magnetic Properties

Inorg. Chem. Front., 2015

Biomolecule pyroglutamic acid has been proficiently harnessed for synthesizing a family of three ... more Biomolecule pyroglutamic acid has been proficiently harnessed for synthesizing a family of three isostructural M4Cu8 dodecanuclear symmetric clusters, which after structural characterization were subjected to magnetic analyses.

Research paper thumbnail of Recent Progress in the Realm of Homonuclear Ln6 Single molecule magnets: Structural Overview and Synthetic Approaches

Proceedings of the Indian National Science Academy, 2015

The synthetic approaches to design hexanuclear Lanthanide-based single molecule magnets are demon... more The synthetic approaches to design hexanuclear Lanthanide-based single molecule magnets are demonstrated in detail. Extensive analysis of the reported hexanuclear systems provides vital insight for controlling the relaxation dynamics of Ln(III)-based SMMS. The assembly of hexanuclear lanthanide-based SMMs employing several ligands is summarized. Favorable structural units could be exploited as motifs in the formation of novel Ln(III)-based SMMs, slow magnetic relaxation feature being the principal focus for them. This review will span a number of hexanuclear homometallic 4fcomplexes, which have been critical in the understanding of the manner in which the lanthanide centers in a complex interact magnetically. Heterometallic 3d-4f complexes which also present hexanuclearity are purposefully evaded to merely streamline and simplify the discussion in a much focused manner. Hexanuclear lanthanide model has particularly been the recent focus of attention to study and comprehend the magnetic coupling in 4f systems. This is to draw imperative conclusions concerning the most effective super-exchange pathways permitting the most efficient intracomplex interactions by demonstrating the research developed in the last few years on the fascinating field of Ln 6-based SMMs with precise emphasis on how recent studies tend to address the issue of relaxation dynamics in these systems from synthetic point of view.

Research paper thumbnail of Framework-Flexibility Driven Selective Sorption of p-Xylene over Other Isomers by a Dynamic Metal-Organic Framework

Scientific Reports, 2014

Chemical separation has great importance in industrial applications. Separation of xylene isomers... more Chemical separation has great importance in industrial applications. Separation of xylene isomers still prevails to be one of the most important challenges in chemical industry, due to the large amount of commercial use of p-xylene in the production of beverage bottles, fibers and films. A novel Zn(II)-based dynamic coordination framework based on flexible ether-linkage, exhibiting selective adsorption of p-Xylene over its congener C 8-alkyl aromatic isomers at ambient conditions is reported. Notably, no dynamic structure based MOF compound is known in the literature which shows clear preference of p-xylene over other isomers. This type of framework-breathing and guest-induced reversible solid-state structural transformations with unique adsorption selectivity can be exploited purposefully to develop smart functional host materials capable of industrially important chemical separations.

Research paper thumbnail of Gas Adsorption, Magnetism, and Single-Crystal to Single-Crystal Transformation Studies of a Three-Dimensional Mn(II) Porous Coordination Polymer

Crystal Growth & Design, 2014

A porous coordination polymer {[Mn2(DBIBA)3]×(NO3)•3DMF•4H2O}n (1) [DBIBAH = 3,5-di(1H-benzo[d]im... more A porous coordination polymer {[Mn2(DBIBA)3]×(NO3)•3DMF•4H2O}n (1) [DBIBAH = 3,5-di(1H-benzo[d]imidazol-1-yl)benzoic acid] has been synthesized solvothermally and structurally characterized by single-crystal X-ray diffraction. This compound shows significant selective CO2 uptake at low temperature. 1 exhibits antiferromagnetic properties below 17 K, confirmed by magnetic susceptibility measurements. Four new coordination polymers: {[Mn2(DBIBA)3]•ClO4•3DMF•3H2O}n (2), {[Mn2(DBIBA)3]×Cl×DMF×H2O}n (3), {[Mn2(DBIBA)3]×NO3×CH3OH×7H2O}n (4) and {[Mn2(DBIBA)3]×NO3×2CH3COCH3×H2O}n (5), have been synthesized from 1 via anion/solvent exchange protocols at room temperature.

Research paper thumbnail of Structural Dynamism and Controlled Chemical Blocking/Unblocking of Active Coordination Space of a Soft Porous Crystal

Inorganic Chemistry, 2013

Identification code Compound 1⊃ ⊃ ⊃ ⊃THF Empirical formula C70 H70 Cd3 O24 Formula weight 1632.46... more Identification code Compound 1⊃ ⊃ ⊃ ⊃THF Empirical formula C70 H70 Cd3 O24 Formula weight 1632.46 Temperature 200(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P 2/c Unit cell dimensions a = 15.4481(10) Å b = 11.4391(7) Å c = 19.1156(13) Å α= 90°. β= 94.6250(10)°. γ = 90°. Volume 3367.0(4) Å 3 Z 2 Density (calculated) 1.610 Mg/m 3 Absorption coefficient 1.020 mm-1 F(000) 1652 Crystal size 0.14 x 0.10 x 0.08 mm 3 Theta range for data collection 3.27 to 27.00°. Index ranges-19<=h<=18,-14<=k<=14,-24<=l<=23 Reflections collected 29798 Independent reflections 7318 [R(int) = 0.0238] Completeness to theta = 25.00° 99.50% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9229 and 0.8704 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7318 / 0 / 447 Goodness-of-fit on F 2 0.993 Final R indices [I>2sigma(I)] R1 = 0.0342, wR2 = 0.0940 R indices (all data) R1 = 0.0386, wR2 = 0.0985 Largest diff. peak and hole 2.139 and-1.083 e.Å-3 109.1 O(5)-Cd(2)#3 2.361(2) C(1)-O(1)-Cd(2) 130.3(2) O(9)-Cd(2)#4 2.275(2) C(1)-O(2)-Cd(1) 134.7(2) O(9)-Cd(2)#5 2.548(2) C(27)-O(3)-Cd(1) 148.2(2) O(10)-Cd(1)#5 2.311(2) C(27)-O(3)-Cd(2)#3 91.97(17) O(10)-Cd(2)#5 2.391(2) Cd(1)-O(3)-Cd(2)#3 97.80(8) Cd(1)-O(2)#3 2.217(2) C(27)-O(5)-Cd(2)#3 92.04(18) Cd(1)-O(3)#3 2.300(2) C(8)-O(6)-C(5) 116.4(3) Cd(1)-O(10)#6 2.311(2) C(12)-O(7)-C(14) 119.1(3) Cd(1)-O(10)#7 2.311(2) C(20)-O(8)-C(10) 119.2(3) Cd(2)-O(9)#4 2.275(2) C(24)-O(9)-Cd(2)#4 168.2(2) Cd(2)-O(3)#3 2.350(2) C(24)-O(9)-Cd(2)#5 90.00(17) Cd(2)-O(5)#3 2.361(2) Cd(2)#4-O(9)-Cd(2)#5 98.72(8) Cd(2)-O(10)#6 2.391(2) C(24)-O(10)-Cd(1)#5 151.4(2) Cd(2)-O(9)#6 2.548(2) C(24)-O(10)-Cd(2)#5 97.13(17) Cd(2)-C(27)#3 2.711(3) Cd(1)#5-O(10)-Cd(2)#5 96.33(7) C(28)-O(11)-C(31) 108.7(6) O(2)-C(1)-O(1) 126.2(3) C(35)-O(12)-C(32) 92.1(8) O(2)-C(1)-C(2) 117.2(3) O(2)-Cd(1)-O(2)#3 96.84(14) O(1)-C(1)-C(2) 116.6(3) O(2)-Cd(1)-O(3) 170.61(10) C(3)-C(2)-C(7) 119.0(3) O(2)#3-Cd(1)-O(3) 90.70(9) C(3)-C(2)-C(1) 120.7(3) O(2)-Cd(1)-O(3)#3 90.70(9) C(7)-C(2)-C(1) 120.3(3) O(2)#3-Cd(1)-O(3)#3 170.61(10) C(2)-C(3)-C(4) 120.7(3) O(3)-Cd(1)-O(3)#3 82.38(12) C(2)-C(3)-H(4) 119.7 O(2)-Cd(1)-O(10)#6 89.92(8) C(4)-C(3)-H(4) 119.7 O(2)#3-Cd(1)-O(10)#6 96.33(8) C(5)-C(4)-C(3) 119.2(3) O(3)-Cd(1)-O(10)#6 94.82(8) C(5)-C(4)-H(5) 120.4 O(3)#3-Cd(1)-O(10)#6 78.02(7) C(3)-C(4)-H(5) 120.4 O(2)-Cd(1)-O(10)#7 96.33(8) C(4)-C(5)-C(6) 121.4(3) O(2)#3-Cd(1)-O(10)#7 89.92(8) C(4)-C(5)-O(6) 119.1(3) O(3)-Cd(1)-O(10)#7 78.02(7) C(6)-C(5)-O(6) 119.6(3) O(3)#3-Cd(1)-O(10)#7 94.82(8) C(5)-C(6)-C(7) 119.1(3) O(10)#6-Cd(1)-O(10)#7 170.59(12) C(5)-C(6)-H(24) 120.5 O(1)-Cd(2)-O(4) 157.30(9) C(7)-C(6)-H(24) 120.5 O(1)-Cd(2)-O(9)#4 82.32(8)

Research paper thumbnail of Bi-porous metal–organic framework with hydrophilic and hydrophobic channels: selective gas sorption and reversible iodine uptake studies

Research paper thumbnail of Toxic Aromatics Induced Responsive Facets for a Pore Surface Functionalized Luminescent Coordination Polymer

Inorganic chemistry, Jan 31, 2017

A luminescent coordination polymer was synthesized based on a linker prefunctionalization-based d... more A luminescent coordination polymer was synthesized based on a linker prefunctionalization-based design principle coupled with an appropriate template selection protocol adopted during crystallization. Luminescent linker derived photoluminescence emission signature together with the reversibly dynamic host polymer exhibited a unique response toward environmentally toxic aromatics in the solid state, arguably crucial for the designed development of toxin-responsive solid materials.

Research paper thumbnail of Porphyrin based metal-organic framework films: nucleation and growth

Journal of Materials Chemistry A, 2020

Integration of porphyrin based metal-organic frameworks (PP-MOFs) on a solid surface has emerged ... more Integration of porphyrin based metal-organic frameworks (PP-MOFs) on a solid surface has emerged as a key advancement in terms of exploring their promising applications. However, a great challenge remains unmet when it comes to successfully fabricating a PP-MOF film with crystallinity, controllable orientation, adjustable morphology and thickness, all sustained in one. Herein, for the first time, vaporassisted conversion (VAC) was developed as a facile and versatile technique to fabricate functional PP-MOF films on various substrates related to different application requirements. To understand the nucleation and growth mechanism, a number of fabrication methods were leveraged to prepare the PP-MOF films, thanks to an assortment of PP-MOFs varying from two-dimensional (2D) to threedimensional (3D) scaffolds. The studies show that PP-MOF films are likely to display different nucleation and growth processes following different deposition approaches. This study demonstrates the pros and cons of different methods in the fabrication of functional PP-MOF films, potentially offering critical tools and reference points for the preparation of next-generation functional MOF thin films in general.

Research paper thumbnail of Crystal engineered hybrid ultramicroporous materials for single-step ethylene purification from C2–CO2 ternary mixture

Acta Crystallographica Section A Foundations and Advances

Mankind is now in the "age of gas"[1] and there are urgent needs in gas purification that will li... more Mankind is now in the "age of gas"[1] and there are urgent needs in gas purification that will likely only be solved by a new generation of physisorbent porous materials that offer reduced cost and superior performance. Engaging the principles of crystal engineering, hybrid ultramicroporous materials, HUMs (pore size < 0.7 nm) [2], by means of combining small pores (< 0.7 nm) with strong electrostatics offer an ideal sorbent platform suited for tight-fit of the target sorbate, resulting in performance benchmarks over the recent years [3, 4]. However, due to narrow pore networks imposing steric restrictions, crystal engineering of modular HUMs on account of organic ligand functionalisation has remained largely elusive. Moving one step ahead of the synergistic sorbent separation technology [5], herein we address single-step purification of ethylene (C 2 H 4), the highest volume product of the chemical industry, by crystal engineering of two HUMs of formula [Ni(pyz-NH 2) 2 (MF 6)] n (pyz-NH 2 = aminopyrazine, 17; M = Si, Ti), MFSIX-17-Ni [6]. Isostructural pyrazine analogues (SIFSIX-3-Zn [7], SIFSIX-3-Ni [8]) are the benchmark physisorbents for trace carbon capture but are unsuited for acetylene capture. No single physisorbent has the requisite selectivity to purify C 2 H 4 from ternary C 2-CO 2 mixtures (C 2 H 4 /C 2 H 2 /CO 2) under ambient conditions until now. Indeed, both MFSIX-17-Ni sorbents produce polymer grade ethylene (> 99.95% purity) from a 1:1:1 ternary mixture (Figure 1). Regarding insights for the future, we attribute the observed properties to the unusual binding sites in MFSIX-17-Ni that offer comparable affinity to both CO 2 and C 2 H 2 , thereby enabling coadsorption of C 2 H 2 and CO 2. In situ synchrotron x-ray diffraction, in situ IR spectroscopy and molecular modelling provide insight into these binding sites and why they differ from those of the pyrazine-linked materials. Figure 1. Schematic illustration of MFSIX-17-Ni that exhibits single-step C 2 H 4 purification by simulatneous CO 2 and C 2 H 2 removal.

Research paper thumbnail of Amino‐Functionalised Hybrid Ultramicroporous Materials that Enable Single‐Step Ethylene Purification from a Ternary Mixture

Angewandte Chemie International Edition, 2021

Pyrazine-linked hybrid ultramicroporous (pore size < 7)m aterials (HUMs) offer benchmark performa... more Pyrazine-linked hybrid ultramicroporous (pore size < 7)m aterials (HUMs) offer benchmark performance for trace carbon capture thanks to strong selectivity for CO 2 over small gas molecules,i ncluding light hydrocarbons.T hat the prototypal pyrazine-linked HUMs are amenable to crystal engineering has enabled second generation HUMs to supersede the performance of the parent HUM, SIFSIX-3-Zn, mainly through substitution of the metal and/or the inorganic pillar.Herein, we report that two isostructural aminopyrazinelinked HUMs, MFSIX-17-Ni (17 = aminopyrazine;M = Si, Ti), whichwehad anticipated would offer even stronger affinity for CO 2 than their pyrazine analogs,u nexpectedly exhibit reduced CO 2 affinity but enhanced C 2 H 2 affinity. MFSIX-17-Ni are consequently the first physisorbents that enable singlestep production of polymer-grade ethylene (> 99.95 %f or SIFSIX-17-Ni)from aternary equimolar mixture of ethylene, acetylene and CO 2 thanks to coadsorption of the latter two gases.W ea ttribute this performance to the very different binding sites in MFSIX-17-Ni versus SIFSIX-3-Zn.

Research paper thumbnail of Spiers Memorial Lecture: Coordination networks that switch between nonporous and porous structures: an emerging class of soft porous crystals

Faraday Discussions, 2021

This review of soft coordination networks that undergo guest-induced switching between nonporous ... more This review of soft coordination networks that undergo guest-induced switching between nonporous and porous structures addresses switching mechanisms and their potential utility.

Research paper thumbnail of Trace CO 2 capture by an ultramicroporous physisorbent with low water affinity

Science Advances, 2019

The first sorbent with high CO 2 selectivity and poor water affinity addresses need for trace CO ... more The first sorbent with high CO 2 selectivity and poor water affinity addresses need for trace CO 2 remediation in confined spaces.

Research paper thumbnail of Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network, X‐pcu‐5‐Zn, by Pillar‐Ligand Substitution

Angewandte Chemie, 2019

Coordination networks that reversibly switch between closed and open phases are of topical intere... more Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacity for gas storage applications than related rigid porous coordination networks. In order to be of practical utility, the pressures at which switching occurs, the gate-opening and gate-closing pressures. Here we study the effect of linker substitution to fine-tune gate-opening and gate-closing pressure. Specifically, three variants of a previously reported pcu topology MOF, X-pcu-5-Zn, have been prepared. X-pcu-6-Zn, 6 = 1,2-bis(4pyridyl)ethane (bpe), X-pcu-7-Zn, 7 = 1,2-bis(4-pyridyl)acetylene (bpa) and X-pcu-8-Zn, 8 = 4,4'-azopyridine (apy), each exhibited switching isotherms but at different gate-opening pressures. The N2, CO2, C2H2 and C2H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gateopening and gate-closing pressures. This simple design principle enables rational control of the switching behaviour in adsorbent materials.

Research paper thumbnail of Hydrophobic metal-organic frameworks: Potential toward emerging applications

APL Materials, 2019

Barrier materials for flexible bioelectronic implants with chronic stability-Current approaches a... more Barrier materials for flexible bioelectronic implants with chronic stability-Current approaches and future directions APL Materials 7, 050902 (2019);

Research paper thumbnail of Stabilizing Metal–Organic Polyhedra (MOP): Issues and Strategies

Chemistry – An Asian Journal, 2019

Research paper thumbnail of Crystal engineering of dichromate pillared hybrid ultramicroporous materials incorporating pyrazole-based ligands

CrystEngComm, 2018

Short and sterically encumbered pyrazole ligands have led to the first examples of non-interpenet... more Short and sterically encumbered pyrazole ligands have led to the first examples of non-interpenetrated, dichromate pillared hybrid ultramicroporous materials.

Research paper thumbnail of Coordination Network That Reversibly Switches between Two Nonporous Polymorphs and a High Surface Area Porous Phase

Journal of the American Chemical Society, 2018

We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn 2 (DMTDC) 2 (dpe... more We report a 2-fold interpenetrated primitive cubic (pcu) network X-pcu-5-Zn, [Zn 2 (DMTDC) 2 (dpe)] (H 2 DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylic acid, dpe = 1,2-di(4-pyridyl)ethylene), that exhibits reversible switching between an as-synthesized "open" phase, X-pcu-5-Zn-, and two nonporous or "closed" polymorphs, X-pcu-5-Zn- and X-pcu-5-Zn-. There are two unusual features of X-pcu-5-Zn. The first relates to its sorption properties, which reveal that the  form Scheme 1. Structural transformations of X-pcu-5-Zn.

Research paper thumbnail of Recyclable switching between nonporous and porous phases of a square lattice (sql) topology coordination network

Chemical communications (Cambridge, England), Jan 21, 2018

A nonporous square lattice (sql) coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits ... more A nonporous square lattice (sql) coordination network [Co(bipy)2(NCS)2]n (sql-1-Co-NCS) exhibits recyclable switching induced by CO2. The sorption isotherms are stepped with moderate hysteresis, temperature controlled and saturation uptake is fixed. Such switching, which has rarely been observed, offers the promise of exceptional working capacity for gas storage.

Research paper thumbnail of Self-assembled, Fluorine-rich Porous Organic Polymers: A Class of Mechanically Stiff and Hydrophobic Materials

Chemistry (Weinheim an der Bergstrasse, Germany), Jan 29, 2018

Fluorous organic building blocks have been cogently harnessed to develop two self-assembled, hydr... more Fluorous organic building blocks have been cogently harnessed to develop two self-assembled, hydrophobic and fluorinated porous organic polymers (FPOPs) namely, FPOP-100 and FPOP-101. On comprehensive mechanical analyses of these functionalized triazine network polymers, they mark the introduction of mechanical stiffness among all porous organic network materials; recorded stiffness features analogous to their organic-inorganic hybrid polymer analogues, viz. metal-organic frameworks (MOFs). Further, the study presents a new paradigm for the simultaneous installation of mechanical stiffness and high surface hydrophobicity into polymeric organic networks, which has the utilitarian potential to be translated among all porous solids. Control experiments with non-fluorinated congeners could underline the key role of fluorine, in particular, bis(trifluoromethyl)-functionalization behind realizing the dual features of mechanical stiffness and superhydrophobicity.

Research paper thumbnail of Polar Pore Surface Guided Selective CO2 Adsorption in a Prefunctionalized Metal–Organic Framework

Crystal Growth & Design, 2017

Selective CO 2 adsorption over other small gases has been realized in an ultramicroporous metal-o... more Selective CO 2 adsorption over other small gases has been realized in an ultramicroporous metal-organic framework (MOF). In the quest of manifesting such selective carbon capture performance, the pre-functionalized linker strategy has been espoused. A new Zn(II)-based three-dimensional, threefold interpenetrated MOF material [Zn(PBDA)(DPNI)] n .xG (PBDA: 4,4'-((2-(tert-butyl)-1,4-phenylene)bis(oxy))dibenzoic acid; DPNI: N,N'-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide; xG: x number of guest species) with unusual rob topology is synthesized following a typical solvothermal synthesis protocol, which gleans a modest CO 2-selective adsorption trend over its congener gases (saturation CO 2 uptake capacity: 2.39 and 3.44 mmolg-1 , at 298K and 273K; volumetric single component isotherm based separation ratios at 0.2 bar: 189.4 (CO 2 /N 2 , 256.5 (CO 2 /H 2), 12.3 (CO 2 /CH 4); at 1 bar: 6.8 (CO 2 /N 2 , 17.1 (CO 2 /H 2), 7.1 (CO 2 /CH 4)). The compound also exhibits selective benzene sorption over its aliphatic C 6-analogue cyclohexane. The structure-property correlation guided results supported by theoretical introspection further emphasize the omnipresent role of crystal engineering principles behind culmination of such targeted properties in the nanoporous MOF domain, to realize selective sorption facets.

Research paper thumbnail of Chiral Biomolecule Based Dodecanuclear Dysprosium(III)-Copper(II) Clusters: Structural Analyses and Magnetic Properties

Inorg. Chem. Front., 2015

Biomolecule pyroglutamic acid has been proficiently harnessed for synthesizing a family of three ... more Biomolecule pyroglutamic acid has been proficiently harnessed for synthesizing a family of three isostructural M4Cu8 dodecanuclear symmetric clusters, which after structural characterization were subjected to magnetic analyses.

Research paper thumbnail of Recent Progress in the Realm of Homonuclear Ln6 Single molecule magnets: Structural Overview and Synthetic Approaches

Proceedings of the Indian National Science Academy, 2015

The synthetic approaches to design hexanuclear Lanthanide-based single molecule magnets are demon... more The synthetic approaches to design hexanuclear Lanthanide-based single molecule magnets are demonstrated in detail. Extensive analysis of the reported hexanuclear systems provides vital insight for controlling the relaxation dynamics of Ln(III)-based SMMS. The assembly of hexanuclear lanthanide-based SMMs employing several ligands is summarized. Favorable structural units could be exploited as motifs in the formation of novel Ln(III)-based SMMs, slow magnetic relaxation feature being the principal focus for them. This review will span a number of hexanuclear homometallic 4fcomplexes, which have been critical in the understanding of the manner in which the lanthanide centers in a complex interact magnetically. Heterometallic 3d-4f complexes which also present hexanuclearity are purposefully evaded to merely streamline and simplify the discussion in a much focused manner. Hexanuclear lanthanide model has particularly been the recent focus of attention to study and comprehend the magnetic coupling in 4f systems. This is to draw imperative conclusions concerning the most effective super-exchange pathways permitting the most efficient intracomplex interactions by demonstrating the research developed in the last few years on the fascinating field of Ln 6-based SMMs with precise emphasis on how recent studies tend to address the issue of relaxation dynamics in these systems from synthetic point of view.

Research paper thumbnail of Framework-Flexibility Driven Selective Sorption of p-Xylene over Other Isomers by a Dynamic Metal-Organic Framework

Scientific Reports, 2014

Chemical separation has great importance in industrial applications. Separation of xylene isomers... more Chemical separation has great importance in industrial applications. Separation of xylene isomers still prevails to be one of the most important challenges in chemical industry, due to the large amount of commercial use of p-xylene in the production of beverage bottles, fibers and films. A novel Zn(II)-based dynamic coordination framework based on flexible ether-linkage, exhibiting selective adsorption of p-Xylene over its congener C 8-alkyl aromatic isomers at ambient conditions is reported. Notably, no dynamic structure based MOF compound is known in the literature which shows clear preference of p-xylene over other isomers. This type of framework-breathing and guest-induced reversible solid-state structural transformations with unique adsorption selectivity can be exploited purposefully to develop smart functional host materials capable of industrially important chemical separations.

Research paper thumbnail of Gas Adsorption, Magnetism, and Single-Crystal to Single-Crystal Transformation Studies of a Three-Dimensional Mn(II) Porous Coordination Polymer

Crystal Growth & Design, 2014

A porous coordination polymer {[Mn2(DBIBA)3]×(NO3)•3DMF•4H2O}n (1) [DBIBAH = 3,5-di(1H-benzo[d]im... more A porous coordination polymer {[Mn2(DBIBA)3]×(NO3)•3DMF•4H2O}n (1) [DBIBAH = 3,5-di(1H-benzo[d]imidazol-1-yl)benzoic acid] has been synthesized solvothermally and structurally characterized by single-crystal X-ray diffraction. This compound shows significant selective CO2 uptake at low temperature. 1 exhibits antiferromagnetic properties below 17 K, confirmed by magnetic susceptibility measurements. Four new coordination polymers: {[Mn2(DBIBA)3]•ClO4•3DMF•3H2O}n (2), {[Mn2(DBIBA)3]×Cl×DMF×H2O}n (3), {[Mn2(DBIBA)3]×NO3×CH3OH×7H2O}n (4) and {[Mn2(DBIBA)3]×NO3×2CH3COCH3×H2O}n (5), have been synthesized from 1 via anion/solvent exchange protocols at room temperature.

Research paper thumbnail of Structural Dynamism and Controlled Chemical Blocking/Unblocking of Active Coordination Space of a Soft Porous Crystal

Inorganic Chemistry, 2013

Identification code Compound 1⊃ ⊃ ⊃ ⊃THF Empirical formula C70 H70 Cd3 O24 Formula weight 1632.46... more Identification code Compound 1⊃ ⊃ ⊃ ⊃THF Empirical formula C70 H70 Cd3 O24 Formula weight 1632.46 Temperature 200(2) K Wavelength 0.71073 Å Crystal system Monoclinic Space group P 2/c Unit cell dimensions a = 15.4481(10) Å b = 11.4391(7) Å c = 19.1156(13) Å α= 90°. β= 94.6250(10)°. γ = 90°. Volume 3367.0(4) Å 3 Z 2 Density (calculated) 1.610 Mg/m 3 Absorption coefficient 1.020 mm-1 F(000) 1652 Crystal size 0.14 x 0.10 x 0.08 mm 3 Theta range for data collection 3.27 to 27.00°. Index ranges-19<=h<=18,-14<=k<=14,-24<=l<=23 Reflections collected 29798 Independent reflections 7318 [R(int) = 0.0238] Completeness to theta = 25.00° 99.50% Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.9229 and 0.8704 Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 7318 / 0 / 447 Goodness-of-fit on F 2 0.993 Final R indices [I>2sigma(I)] R1 = 0.0342, wR2 = 0.0940 R indices (all data) R1 = 0.0386, wR2 = 0.0985 Largest diff. peak and hole 2.139 and-1.083 e.Å-3 109.1 O(5)-Cd(2)#3 2.361(2) C(1)-O(1)-Cd(2) 130.3(2) O(9)-Cd(2)#4 2.275(2) C(1)-O(2)-Cd(1) 134.7(2) O(9)-Cd(2)#5 2.548(2) C(27)-O(3)-Cd(1) 148.2(2) O(10)-Cd(1)#5 2.311(2) C(27)-O(3)-Cd(2)#3 91.97(17) O(10)-Cd(2)#5 2.391(2) Cd(1)-O(3)-Cd(2)#3 97.80(8) Cd(1)-O(2)#3 2.217(2) C(27)-O(5)-Cd(2)#3 92.04(18) Cd(1)-O(3)#3 2.300(2) C(8)-O(6)-C(5) 116.4(3) Cd(1)-O(10)#6 2.311(2) C(12)-O(7)-C(14) 119.1(3) Cd(1)-O(10)#7 2.311(2) C(20)-O(8)-C(10) 119.2(3) Cd(2)-O(9)#4 2.275(2) C(24)-O(9)-Cd(2)#4 168.2(2) Cd(2)-O(3)#3 2.350(2) C(24)-O(9)-Cd(2)#5 90.00(17) Cd(2)-O(5)#3 2.361(2) Cd(2)#4-O(9)-Cd(2)#5 98.72(8) Cd(2)-O(10)#6 2.391(2) C(24)-O(10)-Cd(1)#5 151.4(2) Cd(2)-O(9)#6 2.548(2) C(24)-O(10)-Cd(2)#5 97.13(17) Cd(2)-C(27)#3 2.711(3) Cd(1)#5-O(10)-Cd(2)#5 96.33(7) C(28)-O(11)-C(31) 108.7(6) O(2)-C(1)-O(1) 126.2(3) C(35)-O(12)-C(32) 92.1(8) O(2)-C(1)-C(2) 117.2(3) O(2)-Cd(1)-O(2)#3 96.84(14) O(1)-C(1)-C(2) 116.6(3) O(2)-Cd(1)-O(3) 170.61(10) C(3)-C(2)-C(7) 119.0(3) O(2)#3-Cd(1)-O(3) 90.70(9) C(3)-C(2)-C(1) 120.7(3) O(2)-Cd(1)-O(3)#3 90.70(9) C(7)-C(2)-C(1) 120.3(3) O(2)#3-Cd(1)-O(3)#3 170.61(10) C(2)-C(3)-C(4) 120.7(3) O(3)-Cd(1)-O(3)#3 82.38(12) C(2)-C(3)-H(4) 119.7 O(2)-Cd(1)-O(10)#6 89.92(8) C(4)-C(3)-H(4) 119.7 O(2)#3-Cd(1)-O(10)#6 96.33(8) C(5)-C(4)-C(3) 119.2(3) O(3)-Cd(1)-O(10)#6 94.82(8) C(5)-C(4)-H(5) 120.4 O(3)#3-Cd(1)-O(10)#6 78.02(7) C(3)-C(4)-H(5) 120.4 O(2)-Cd(1)-O(10)#7 96.33(8) C(4)-C(5)-C(6) 121.4(3) O(2)#3-Cd(1)-O(10)#7 89.92(8) C(4)-C(5)-O(6) 119.1(3) O(3)-Cd(1)-O(10)#7 78.02(7) C(6)-C(5)-O(6) 119.6(3) O(3)#3-Cd(1)-O(10)#7 94.82(8) C(5)-C(6)-C(7) 119.1(3) O(10)#6-Cd(1)-O(10)#7 170.59(12) C(5)-C(6)-H(24) 120.5 O(1)-Cd(2)-O(4) 157.30(9) C(7)-C(6)-H(24) 120.5 O(1)-Cd(2)-O(9)#4 82.32(8)

Research paper thumbnail of Bi-porous metal–organic framework with hydrophilic and hydrophobic channels: selective gas sorption and reversible iodine uptake studies

Research paper thumbnail of Toxic Aromatics Induced Responsive Facets for a Pore Surface Functionalized Luminescent Coordination Polymer

Inorganic chemistry, Jan 31, 2017

A luminescent coordination polymer was synthesized based on a linker prefunctionalization-based d... more A luminescent coordination polymer was synthesized based on a linker prefunctionalization-based design principle coupled with an appropriate template selection protocol adopted during crystallization. Luminescent linker derived photoluminescence emission signature together with the reversibly dynamic host polymer exhibited a unique response toward environmentally toxic aromatics in the solid state, arguably crucial for the designed development of toxin-responsive solid materials.

Research paper thumbnail of Porphyrin based metal-organic framework films: nucleation and growth

Journal of Materials Chemistry A, 2020

Integration of porphyrin based metal-organic frameworks (PP-MOFs) on a solid surface has emerged ... more Integration of porphyrin based metal-organic frameworks (PP-MOFs) on a solid surface has emerged as a key advancement in terms of exploring their promising applications. However, a great challenge remains unmet when it comes to successfully fabricating a PP-MOF film with crystallinity, controllable orientation, adjustable morphology and thickness, all sustained in one. Herein, for the first time, vaporassisted conversion (VAC) was developed as a facile and versatile technique to fabricate functional PP-MOF films on various substrates related to different application requirements. To understand the nucleation and growth mechanism, a number of fabrication methods were leveraged to prepare the PP-MOF films, thanks to an assortment of PP-MOFs varying from two-dimensional (2D) to threedimensional (3D) scaffolds. The studies show that PP-MOF films are likely to display different nucleation and growth processes following different deposition approaches. This study demonstrates the pros and cons of different methods in the fabrication of functional PP-MOF films, potentially offering critical tools and reference points for the preparation of next-generation functional MOF thin films in general.

Research paper thumbnail of Metal-organic framework based carbon capture and purification technologies for clean environment

Metal-organic framework based carbon capture and purification technologies 2.2.2 CO 2 selectivity... more Metal-organic framework based carbon capture and purification technologies 2.2.2 CO 2 selectivity, S ads (CO 2 ) CO 2 selectivity for a sorbent defines the sorption uptake ratio of CO 2 over another gas under a given set of conditions. Selectivity versus nitrogen (S CN ) is relevant with respect to postcombustion C-capture whereas selectivity versus methane (S CM ) is particularly relevant for NG purification. As revealed by 2, a fivefold increase in S CN , for example, from 100 to 500, would be expected to significantly reduce C-capture expense per tonne ( . 45 to B30h t 21 CO 2 ) . Selectivity also impacts the purity of adsorbed gas and levels in the outlet (effluent) gas stream. For a binary mixture, the adsorption selectivity (S ads or α ij ) is defined as follows

Research paper thumbnail of Cadmium-based Catalysts