Divergent Structural Transformations in 3D Ag(I) Porous Coordination Polymers Induced by Solvent and Anion Exchanges

Abstract

Two series of ten 3D porous coordination polymers (PCPs), [Ag­(L434)]­(BF4)­(DMF)2 (1·BF 4 ·DMF), [Ag­(L434)]­(BF4)­(CH3CN)2 (1·BF 4 ·CH 3 CN), [Ag­(L434)]­(BF4)­(DMA)­(CH3OH) (1·BF 4 ·DMA/CH 3 OH), [Ag­(L434)]­(ClO4)­(DMF)2 (1·ClO 4 ·DMF), [Ag­(L434)]­(CF3SO3)­(DMF) (1·CF 3 SO 3 ·DMF), [Ag­(L434)]­(ClO4)­(CH3CN)2 (1·ClO 4 ·CH 3 CN), [Ag­(L434)]­(PF6)­(CH3CN)2 (1·PF 6 ·CH 3 CN), [Ag­(L434)]­(CH3SO3)­(DMA) (1·CH 3 SO 3 ·DMA), [Ag­(L434)]­(CF3SO3)­(DMA) (1·CF 3 SO 3 ·DMA), and [Ag2(L434)2]­(BF4)2(CH3OH)2 (2·BF 4 ·CH 3 OH), have been prepared via assembling 3,5-bis­(4-pyridyl)-4-(3-pyridyl)-1,2,4-triazole (L434) with Ag­(I) salts in different solvent media. All these PCPs possess 3D porous cationic frameworks, exhibiting irl topology for 2·BF 4 ·CH 3 OH and sra topology for others (1·anion·solvent) with the same point symbol of (42.63.8). Solvent-induced structural transformations between the topo-isomeric 1·BF 4 ·solvent and 2·BF 4 ·CH 3 OH show drastic deformations of the 3D host frameworks and concomitant solvent exchanges. Three cycles of anion-induced structural conversions involving 1·anion·DMF, 1·anion·CH 3 CN, and 1·anion·DMA isoreticular structures are also observed, in which the mother frameworks are almost unchanged during the anion exchanges. These two types of structural transformations occur upon different external stimuli (solvent and anion), which are accompanied by significant changes in the shape of channels and the volume of voids.

A Highly Efficient Coordination Polymer for Selective Trapping and Sensing of Perrhenate/Pertechnetate

“…A possible explanation is that the CO 3 2– anion could strongly interact with Ag­(I) center to break the charge transfer between metal and ligand. , Therefore, the fluorescence emission is likely to derive from ligand-centered π–π* transitions (Figure S6). As for NO 2 – ion, the luminescence intensity slightly increases by 10.5%. We may conclude that, the incorporated nitrite acts as electron-donating moiety to generate hydrogen-bonding interaction with the ligand, promoting the electron transfer between metal and ligand. , Moreover, by adding the simulated Hanford LAW melter recycle stream (100 μL) to TJNU-302 (1 mg) suspension, the luminescence intensity will increase by 14.6% (Figure S8).…”

“…47,48 Therefore, the fluorescence emission is likely to derive from ligandcentered π−π* transitions (Figure S6). 49 As for NO 2 − ion, the luminescence intensity slightly increases by 10.5%. We may conclude that, the incorporated nitrite acts as electrondonating moiety to generate hydrogen-bonding interaction with the ligand, promoting the electron transfer between metal and ligand.…”

Chiral Coordination Polymers from a New 2-Deoxy-d-ribose Derivative Linker: Syntheses, Structures, and Fe3+ Fluorescent Probe Functions

“…Methanol molecules involved in hydrogen bonds in metal complexes may be lost at higher temperatures . Some other reported CPs and metal complexes lost CH 3 OH solvent at lower temperatures. − Half of the methanol molecules in 3 and 4 form C–H···O and O–H···N hydrogen bonds with the ligands (Table S2). The half of the solvent methanol molecules in 3 and 4 lost before the decomposition of the CP skeletons might be those not involved in H-bonds with the ligands, and the other half of the solvent molecules should be those forming H-bonds with the ligands and should depart together with the decomposition of the CP skeletons.…”

Temperature-Induced Structural Transformations of Lanthanide Coordination Polymers Based on a Semirigid Tricarboxylic Acid Ligand: Crystal Structures and Luminescence Properties

“…Obviously, the enhancement of their emission intensity at different complexes can be attributed to the increased rigidity of the ligand when bound to the Eu(III) center, which will effectively prevent the thermal deactivation pathways. 39 Meantime, comparing the spectra of complexes Eu(III) and Tb(III), it is not difficult to find that the emission intensity follows the trend Tb(III) > Eu(III), which signifies that the energy transfer from the H 3 TCMA + to Tb(III) is more effective than to Eu(III). Moreover, the lifetimes (τ 1 = 626.6 μs, τ 3 = 612.7 μs, τ 5 = 439.8 μs) of Eu 3+ complex has relatively shorter than the Tb(III) complexes (τ 2 = 1023.0 μs, τ 4 = 994.0 μs, τ 6 = 812.1 μs), which also shows that the Tb(III) complexes are more preferably sensitized.…”