IRMOF-10, derived from biphenyl-4,4'-dicarboxylic acid and zinc, is a prototype for an open cubic structure prone to interpenetration. Interpenetration can compromise MOF pore volume and surface area which drives the need to develop strategies to synthesize non-interpenetrated MOFs. In this work, an additive design strategy was employed to suppress interpenetration of IRMOF-10. The presence of the additive during traditional solvothermal synthesis yielded an activated material with the highest surface area reported to date and enabled the determination of the single crystal structure. monitoring of the nucleation of crystals under polarized light provided insights into the mechanism behind interpenetration in the IRMOF-9/10 system. This work provides a roadmap to suppress interpenetration more generically in other MOFs and achieve improved surface areas and pore volumes for this prominent class of porous sorbents.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/d4cc03138e | DOI Listing |
Chem Commun (Camb)
August 2024
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan, 48109, USA.
IRMOF-10, derived from biphenyl-4,4'-dicarboxylic acid and zinc, is a prototype for an open cubic structure prone to interpenetration. Interpenetration can compromise MOF pore volume and surface area which drives the need to develop strategies to synthesize non-interpenetrated MOFs. In this work, an additive design strategy was employed to suppress interpenetration of IRMOF-10.
View Article and Find Full Text PDFChemistry
December 2023
Department of Chemistry WBSH5053, Youngstown State University, Youngstown, OH 44555, USA.
One of the iconic characteristics of metal-organic frameworks (MOFs) is the possesssion of guest-accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size.
View Article and Find Full Text PDFDalton Trans
August 2023
Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, School of Chemical and Material Science, Shanxi Normal University, Taiyuan 030031, China.
Three novel naphthalenediimide-based (NDI-based) coordination polymers (CPs), namely [Cd(3-PMNDI)(2,2'-BPDC)] (1), [Cd(3-PMNDI)(4,4'-BPDC)(HO)]·DMF (2) and [Cd(3-PMNDI)(4,4'-SDC)] (3) (2,2'-HBPDC = 2,2'-biphenyldicarboxylic acid, 4,4'-HBPDC = 4,4'-biphenyldicarboxylic acid, 4,4'-HSDC = 4,4'-stilbenedicarboxylic acid, 3-PMNDI = ,'-bis(3-pyridylmethyl)-1,4,5,8-naphthalenediimide, and DMF = ,'-dimethylformamide), have been designed and synthesized here from electron-deficient PMNDI (electron acceptors, EAs) and electron-rich aromatic carboxylic acids (electron donors, EDs) in the presence of cadmium ions. The introduction of aromatic carboxylic acids with different sizes and conjugation degrees leads to the generation of a two-dimensional (2D) layer in 1, a two-fold interpenetrated three-dimensional (3D) network in 2 and an eight-fold interpenetrated 3D framework in 3. Furthermore, the use of distinct electron-donating aromatic carboxylic acids and the consequent different numbers and strengths of lone pair-π and π-π interactions in the interfacial contacts of EDs/EAs give rise to distinct intermolecular charge transfer (ICT) and initial colors of the three CPs, and consequently cause different photoinduced intermolecular electron transfer (PIET) and distinguishing photo-responsive behaviors (weak photochromic performance for 1, excellent photochromic properties for 2 and non-photochromism for 3).
View Article and Find Full Text PDFRSC Adv
May 2021
School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology Zhenjiang Jiangsu 212003 China
Three new luminescent metal-organic frameworks (LMOFs), [Zn(tppa)(ndc)] (1), [Cd(tppa)(oba)] (2), [Zn(tppa)(bpdc)] (3) (tppa = tri(4-pyridylphenyl)amine, ndc = 1,4-naphthalenedicarboxylic acid, oba = 4,4'-oxydibenzoic acid, bpdc = 4,4'-biphenyldicarboxylic acid) have been synthesized by solvothermal method. Complexes 1 and 2 are 2-D two-fold interpenetrating structures, aligning into a 3-D structure through C-H⋯π stacking interactions, while 3 is a 5-fold interpenetrating three-dimensional structure. The internal quantum yields (IQYs) of complexes 1-3 are 32.
View Article and Find Full Text PDFFaraday Discuss
February 2021
Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK.
The reactions of Zn(NO)·6HO with the polycarboxylic acids 1,3-benzenedicarboxylic acid (Hmbdc), 1,4-benzenedicarboxylic acid (Hbdc), 1,3,5-benzenetricarboxylic acid (Hbtc) and 4,4'-biphenyldicarboxylic acid (Hbpdc) in the presence of methyl viologen iodide ([MV]I) in DMF gave anionic frameworks with methyl viologen species incorporated as counter-ions. When the reactions were carried out at 120 °C, the blue products [MV][Zn(mbdc)] (1-ht), [MV][HMV][NMeH][Zn(bdc)]·0.6DMF (2-ht), [MV][Zn(btc)]·DMF (4-ht) and [MV][Zn(bpdc)]·8DMF·10HO (5-ht) were formed, and these were shown to contain the radical cation [MV]˙.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!