ABSTRACT
Water adsorption/desorption cyclability of porous materials is a prerequisite for diverse applications, including atmospheric water harvesting (AWH), humidity autocontrol (HAC), heat pumps and chillers, and hydrolytic catalysis. However, unambiguous molecular insights into the correlation between underlying building blocks and the cyclability are still highly elusive. In this work, by taking advantage of the well-established isoreticular synthetic principle in Zr(IV) metal-organic frameworks (Zr-MOFs), we show that the inherent density of hydrogen atoms in the organic skeleton can play a key role in regulating the water sorption cyclability of MOFs. The ease of isoreticular practice of Zr-MOFs enables the successful syntheses of two pairs of isostructural Zr-MOFs (NU-901 and NU-903, NU-950 and SJTU-9) from pyrene- or benzene-cored carboxylate linkers, which feature scu and sqc topological nets, respectively. NU-901 and NU-950 comprised of pyrene skeletons carrying more hydrogen-bonding anchoring sites show distinctly inferior cyclability as compared with NU-903 and SJTU-9 built of benzene units. Single-crystal X-ray crystallography analysis of the hydrated structure clearly unveils the water molecule-involved interactions with the hydrogen-bonding donors of benzene moieties. Remarkably, NU-903 and SJTU-9 isomers exhibit outstanding water vapor sorption capacities as well as working capacities at the desired humidity range with potential implementations covering indoor humidity control and water harvesting. Our findings uncover the importance of hydrogen-bonding anchoring site engineering of organic scaffold in manipulating the framework durability toward water sorption cycle and will also likely facilitate the rational design and development of highly robust porous materials.
ABSTRACT
Dynamic long-lived multicolor room temperature afterglow and circularly polarized luminescence (CPL) are promising for optoelectronic applications, but integration of these functions into a single-phase chiroptical material is still a difficult and meaningful challenge. Here, a nitrogen-doped benzimidazole molecule 1H-1,2,3-triazolopyridine (Trzpy) showing pure organic room-temperature phosphorescence (RTP) acted as a linker, and then, we propose a chirality-induced coordination assembly strategy to prepare homochiral crystal materials. Two homochiral coordination polymers DCF-10 and LCF-10 not only exhibit multicolor-tunable RTP, the color changed from green to orange under various excitation wavelengths, but also show remarkable excitation-dependent circularly polarized luminescence (CPL), and the dissymmetry factors of CPL in DCF-10 and LCF-10 are 1.8 × 10-3 and 2.4 × 10-3, respectively. Experimental and theoretical studies demonstrated that molecular atmospheres with different aggregation degrees give rise to multiple emission centers for the generation of multicolor-tunable emission. The multicolor-tunable photophysical properties endowed LCF-10 with a huge advantage for multi-level anti-counterfeiting. This work opens up new perspectives for the development and application of color-tunable RTP and CPL.
ABSTRACT
The construction of circularly polarized luminescence (CPL) materials with high porosity and high rigidity is still challenging. Herein, we propose a chiral reticular chemistry strategy to prepare the homochiral porous metal-organic frameworks (MOFs) as CPL-active materials. Two pairs of enantiomeric MOFs are synthesized through the self-assembly of chiral D/L-cam (DL-camphorates) and achiral fluorescent ligand TPB (1,2,4,5-tetra(pyridin-4-yl)benzene). The glum values of Cd-CMOF-D and Cd-CMOF-L were up to 0.010 and 0.009; the high glum values could be compared to those of the partially pure multicomponent self-assembly systems obtained by the complicated process. We further trace the generation and transfer of the hierarchical chirality from chiral molecule to 3D framework, demonstrating that the CPL was dominated by the original molecular chirality rather than the global chirality of the hierarchical structure. Moreover, the single-phase white-light materials with nearly ideal CIE coordinates (0.33, 0.33) were constructed through the introduction of dye emitters into Zn-CMOF (Zn-based chiral MOF). This work provided not only an insightful view of the chirality transfer and disappearance mechanism but also an efficient method for the preparation of the highly porous CPL materials.
ABSTRACT
Two Cd-based supramolecular coordination polymers, [Cd3(CzIP)3(DMF)2] (1) and [Cd2(CzIP)2(DMF)4] (2), were synthesized by using 5-(carbazol-9-yl) isophthalate (CzIP) as ligands. These two compounds exhibit multiple luminescence emissions; apart from fluorescence, time- and temperature-dependent ultralong phosphorescence (RTP) were also achieved under room conditions. Significantly, compound 1 has a long-lived afterglow of 0.93 s at 545 nm under ambient conditions. Compound 2 shows nearly pure white-light emission with CIE coordinates of (0.33, 0.33) via the dual emission of fluorescence and phosphorescence. It has come to our attention that it is the first example of a luminescent coordination polymer with single-phase white-light emission and color-evolution RTP. In addition, the long-lived RTP materials can be used in time-dependent anticounterfeiting and white-light-emitting diodes. Experimental and singlet and triplet state calculations indicate that both C-H···π interaction and inter- and intramolecular charge transfer interactions could be beneficial to the emission of ultralong RTP.
