Exploring Crystal Engineering for Porous Uranyl–Organic Frameworks: Insight into Hydrolysis and In Situ Reaction, Structural Variation‐Dependent Physical Properties

Abstract

= 5-((4-carboxybenzyl)oxy)isophthalic acid, H 4 L 2 = 4,4'-oxydiphthalic acid, and H 2 L 3 = 4,4'-((6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl))dibenzoic acid}, have been designed and synthesized under solvothermal and hydrothermal reaction conditions. All of these ligands are firstly used in the syntheses of uranyl hybrid materials. We investigated the main factors on the uranyl hydrolysis systematically and discussed the in situ reaction mechanism in detail. Furthermore, physical properties of these uranyl complexes are dependent on structural variations, such as unusual solvent-impressionable fivepeak photoluminescence for 2, surface photoelectric behavior as potential p-type semiconductors for 2 and 3, and the remarkable superiorities toward selective removal of dye pollutant for the anionic framework 1 compared with the neutral ones 2 and 3. Results and Discussion SynthesisWith this purpose of exploring the porous UOFs, a series of aromatic polycarboxylate ligands were employed to combine [a] J.

Influence of Pyrazine/Piperazine Based Guest Molecules in the Crystal Structures of Uranyl Thiophene Dicarboxylate Coordination Polymers: Structural Diversities and Photocatalytic Activities for the Degradation of Organic Dye

“…It has been thoroughly studied that most of the uranyl containing compounds emit green light centered near 520 nm, with strong vibronic coupling yielding a well resolved five peak pattern. − For compounds I , II , and IV the conspicuous characteristic emission of green light for uranyl cations (439, 487, 507, 529, and 551 nm for I ; 470, 488, 509, 529, and 552 nm for II ; 405, 451, 497, 523, and 540 nm for IV , respectively, are observed in the spectra) (Figure S3). These emission peaks correspond to the electronic and vibronic transitions of S 11 → S 00 , S 10 → S 0υ (υ = 0–2) and S 11 → S 00 , S 10 → S 0υ (υ = 0–3), respectively . The most intense peak is positioned at 507, 509, and 451 nm for I , II , and IV , respectively.…”

“…The UV–vis spectra of compounds ( I – V ) are shown in Figure S2. All these compounds show characteristic band around 325 and 430 nm which are the characteristic equatorial U–O and axial UO charge transfer bands, respectively, for U VI compounds . The solid state emission spectra for the bulk products under excitation wavelength of 320 nm for compound I , III – V , 345 nm for compound II , were recorded at room temperature.…”

“…Compounds based on the uranyl ion (UO 2 ) 2+ gives rise to a number of interesting structural topologies and functional applications. − Uranyl ion containing compounds have found use in photocatalysis and other related areas. − Normally, the (UO 2 ) 2+ centers have been bonded with sulfonate, − phosphonate, − arsenate, − and mono- or dicarboxylates − forming the structures of different dimensionalities like 1D chains, , 2D sheets, , and 3D frameworks. , In some cases, the N-donor ligands were also employed to enhance the dimensionality of the structures. ,, Also, incorporating uranyl ion with another d-block cation is a common strategy in increasing the dimensionality of the UOF’s . The rigid 4,4′-bipyridine along with its flexible derivatives such as 1,2-bis­(4-pyridyl)­ethane and 4,4′-trimethylene dipyridine have been employed in many of these preparations .…”

Functional Sensing Materials Based on Lanthanide N-Heterocyclic Polycarboxylate Crystal Frameworks for Detecting Thiamines

“…Up to now, it has been well established that the application of the lanthanide coordination polymers as functional luminescent probes for effective detection of biomolecules (thiamine) in water solutions has been rarely reported. ,− Thus, the development of selective and sensitive thiamine chemsensors is urgent.…”