Synthesis, Characterization, and Modeling of a Functional Conjugated Microporous Polymer: CO₂ Storage and Light Harvesting

Abstract

Rationalization of structure and properties of amorphous porous solids at the microscopic level is essential in developing advanced materials. We delineate the structural modeling of a designed tetraphenylethene-based amorphous conjugated microporous polymer TPE-CMP (1) and its gas storage and photophysical properties. The polymer 1 exhibits high specific surface area of 854 m 2 /g. 1 showed appreciable CO 2 (32.4 wt %) uptake at 195 K up to 1 atm and 31.6 wt % at 273 K up to 35 bar. The structural model of 1 obtained through computational methods is quantitatively consistent with experimental observations. The microporous structural model of 1 was further validated by a calculation of CO 2 adsorption isotherm obtained through GCMC simulations. Quantum chemical calculations were employed to understand the nature of interactions of CO 2 with the constituents of the framework 1. π−π interaction with strength of 19 kJ/mol was observed between CO 2 and the phenyl rings of TPE. 1 shows strong turn-on greenish-yellow emission due to the restriction of phenyl ring rotation of TPE node. This framework induced emission (FIE) of microporous polymer 1 is further exploited for light-harvesting applications by noncovalent encapsulation of a suitable acceptor dye, rhodamine B (RhB), in the framework.

Highly Luminescent Microporous Organic Polymer with Lewis Acidic Boron Sites on the Pore Surface: Ratiometric Sensing and Capture of F− Ions

“…BMOP was synthesized by Pd 0 /CuI‐catalyzed Sonogashira CC coupling between tris(4‐bromo‐2,3,5,6‐tetramethylphenyl)boron nodes (Supporting Information, Figure S1) and 4,4′‐diethynylbiphenyl linkers (Supporting Information, Figure S2), as shown in Scheme . The FTIR spectrum of BMOP, which shows bands at 980, 1600, and 2100 cm −1 corresponding to the CB, CC, and CC stretching vibrations, respectively12a, 15 (Supporting Information, Figure S3), confirmed the presence of both node and linker moieties in the polymer. Furthermore, the solid‐state 13 C CP/MAS NMR spectrum shows a moderate signal at 90 ppm assigned to C of the CC bond, suggests bonding of the triarylborane node and 4,4′‐diethynylbiphenyl linker (Figure 1).…”

“…Furthermore, the solid‐state 13 C CP/MAS NMR spectrum shows a moderate signal at 90 ppm assigned to C of the CC bond, suggests bonding of the triarylborane node and 4,4′‐diethynylbiphenyl linker (Figure 1). Other peaks ranging from 120–150 ppm can be assigned to the aromatic C atoms of phenyl rings,12a, 16 and the peak at 19 ppm to aliphatic methyl substituents of the phenyl rings 6a. 17 The presence of boron in BMOP was confirmed by X‐ray photoelectron spectroscopy (XPS).…”

Bimodal Heterogeneous Functionality in Redox‐Active Conjugated Microporous Polymer toward Electrocatalytic Oxygen Reduction and Photocatalytic Hydrogen Evolution

“…Conjugated microporous polymers (CMPs) are an emerging class of porous organic materials, which have demonstrated a treasure trove of applications . Owing to their synthetic diversity and permanent microporosity, CMP materials have gained widespread attention in the realms of energy materials, heterogeneous catalysis, and luminescent materials . Recently, the design of redox‐active CMP materials by integrating electron‐donor and ‐acceptor organic struts has drawn immense interest, as they have shown potential for catalyzing the electrochemical oxygen reduction reaction (ORR), which is a half‐cell reaction in fuel cells and metal–air batteries .…”

“…[39,40] Owing to their synthetic diversitya nd permanent microporosity,C MP materials have gainedw idespread attention in the realmso fe nergy materials, [41,42] heterogeneousc atalysis, and luminescent materials. [35,[43][44][45][46][47] Recently,t he design of redox-activeC MP materials by integratingelectron-donora nd -acceptor organic strutsh as drawnimmense interest, as they have shownp otential forc atalyzingt he electrochemical oxygen reduction reaction (ORR), [22,41] which is ah alf-cell reactioni nf uel cells and metalair batteries. [6,28] Moreover,r edox-activeC MPs were also found to be capable of in situ generation and stabilizationo fm etal nanoparticles (NPs), and subsequently,s uch metal nanoparticle stabilized CMP (NP@CMP) materials have shown significantly improvede lectrocatalytic activities.…”

Design of conjugated microporous polymer nanotubes for efficient benzene molecular adsorptions

“…Although the synthesis of tubular porous networks has made a lot of progress, at atomistic level the structure‐performance relationship and the adsorption mechanism of organic molecules to tube surface have not been illustrated clearly. Currently, the theoretical studies focus on the structures and electronic properties of the pure π‐conjugated polymers . Recently, the electronic properties of novel graphyne‐based and graphene‐based nanotubes have been studied by density functional theory (DFT) calculations .…”