The ADOR (Assembly-Disassembly-Organisation-Reassembly) process for zeolites has been shown to produce a number of previously unknown frameworks inaccessible through conventional synthesis methods. Here, we present successful mechanochemically assisted hydrolysis of germanosilicate zeolite UTL leading to ADOR products under mild conditions, low amounts of solvent and in short reaction times. The expansion of zeolite synthesis into the realm of mechanochemistry opens up feasible pathways regarding the production of these materials, especially for industrial purposes, as well as an exciting application for economical enrichment of materials with the low natural abundance NMR-active isotope of oxygen, 17O. The results from mechanochemically assisted hydrolysis differ from those seen in the traditional ADOR approach differences that can be attributed to a change in solvent availability.The question of quadruple bonding in C2 has emerged as a hot button issue, with opinions sharply divided between the practitioners of Valence Bond (VB) and Molecular Orbital (MO) theory. Here, we have systematically studied the Potential Energy Curves (PECs) of low lying high spin sigma states of C2, N2, Be2 and HC[triple bond, length as m-dash]CH using several MO based techniques such as CASSCF, RASSCF and MRCI. The analyses of the PECs for the 2S+1Σg/u (with 2S + 1 = 1, 3, 5, 7, 9) states of C2 and comparisons with those of relevant dimers and the respective wavefunctions were conducted. We contend that unlike in the case of N2 and HC[triple bond, length as m-dash]CH, the presence of a deep minimum in the 7Σ+ state of C2 and CN+ suggests a latent quadruple bonding nature in these two dimers. Our investigations reveal that the number of bonds in the ground state can be determined for 2nd row dimers by figuring out at what value of spin symmetry a purely dissociative PEC is obtained. For N2 and HC[triple bond, length as m-dash]CH the purely dissociative PEC appears for the septet spin symmetry as compared to that for the nonet in C2. This is indicative of a higher number of bonds between the two 2nd row atoms in C2 as compared to those of N2 and HC[triple bond, length as m-dash]CH. Hence, we have struck a reconciliatory note between the MO and VB approaches. The evidence provided by us can be experimentally verified, thus providing the window so that the narrative can move beyond theoretical conjectures.The organization states of functional molecules have a significant impact on the properties of materials. A variety of approaches have been studied to obtain well-organized molecular assemblies. The present work shows a new non-organized state of isolated and dispersed functional molecules in amorphous flexible covalent organic networks. Redox-active quinone molecules are embedded in the amorphous network polymers. Consecutive reactions between benzoquinone (BQ) and linker molecules generate random network structures through polymerization at different rates and in multiple directions. The low-crystalline stackings of the amorphous network polymers facilitate the formation of nanoflakes through exfoliation in dispersion media. Enhanced electrochemical performances, one of the highest specific capacities in recent studies, were achieved by efficient redox reactions of the quinone moiety. The present noncrystalline approach, low-crystalline stacking of designer amorphous covalent organic networks, can be applied to construct similar nanostructured polymer materials containing functional units.Selective photoreduction of CO2 into a given product is a great challenge but desirable. Inspired by natural photosynthesis occurring in hierarchical networks over non-precious molecular metal catalysts, we demonstrate an integration of single Ni sites into the hexagonal pores of polyimide covalent organic frameworks (PI-COFs) for selective photoreduction of CO2 to CO. The single Ni sites in the hexagonal pores of the COFs serve as active sites for CO2 activation and conversion, while the PI-COFs not only act as a photosensitizer to generate charge carriers but also exert a promoting effect on the selectivity. The optimized PI-COF with a triazine ring exhibits excellent activity and selectivity. A possible intra- and inter-molecular charge-transfer mechanism was proposed, in which the photogenerated electrons in PI-COFs are efficiently separated from the central ring to the diimide linkage, and then transferred to the single Ni active sites, as evidenced by theoretical calculations.Separation of the C8 aromatic isomers, p-xylene (PX), m-xylene (MX), o-xylene (OX) and ethylbenzene (EB), is relevant thanks to their widespread application as chemical feedstocks but challenging because of their similar boiling points and close molecular dimensions. Physisorptive separation could offer an energy-efficient solution to this challenge but sorbents which exhibit strong selectivity for one of the isomers remain a largely unmet challenge despite recent reports of OX or PX selective sorbents with high uptake capacity. For example, the square lattice, sql, topology coordination network [Co(bipy)2(NCS)2] n (sql-1-Co-NCS) exhibits the rare combination of high OX selectivity and high uptake capacity. Herein we report that a crystal engineering approach enabled isolation of the mixed-linker sql coordination network [Co(bipy)(bptz)(NCS)2] n (sql-1,3-Co-NCS, bipy = 4,4'-bipyridine, bptz = 4,4'-bis(4-pyridyl)tetrazine) and study of its C8 vapour and liquid sorption properties. sql-1,3-Co-NCS was found to exhibit high adsorption capacity from liquid xylenes (∼37 wt%) and is to our knowledge the first sorbent to exhibit high selectivity for each of xylene isomer over EB (SOX/EB, SMX/EB, SPX/EB > 5). Insights into the performance of sql-1,3-Co-NCS are gained from structural studies which reveal stacking interactions between electron-deficient bptz linkers and the respective xylenes. sql-1,3-Co-NCS is the first N-donor mixed-linker sql coordination network studied for its gas/vapour sorption properties and represents a large and diverse class of understudied coordination networks.Covalent organic frameworks (COFs) have emerged as a kind of promising material for analytical and biomedical purposes. selleck chemicals However, simultaneous cancer diagnosis and therapy with COFs remain a challenge. We report here a COF-based theranostic nanoplatform by integrating a dye-labeled oligonucleotide onto porphyrin-based COF nanoparticles for highly efficient cancer diagnosis and therapy. The fluorescence of the dye was effectively quenched by the COF through fluorescence resonance energy transfer (FRET). In the presence of biomarker survivin mRNA, more stable duplexes were formed and separated from the COF NPs, enabling the recovery of the fluorescence signal and selective cancer imaging. Under NIR laser irradiation, COF NPs generated abundant reactive oxygen species (ROS) to induce cancer cell apoptosis owing to their crystalline reticular structure. In vitro and in vivo experiments revealed that the nanoplatform has a high specificity and inhibition effect toward cancer cells and solid tumors. Interestingly, prognostic evaluation was also realized with COF-survivin.selleck chemicals