The selective capture of carbon dioxide in the presence of water is an outstanding challenge. Here, we show that the interior of IRMOF-74-III can be covalently functionalized with primary amine (IRMOF-74-III-CH2NH2) and used for the selective capture of CO2 in 65% relative humidity. This study encompasses the synthesis, structural characterization, gas adsorption, and CO2 capture properties of variously functionalized IRMOF-74-III compounds (IRMOF-74-III-CH3, -NH2, -CH2NHBoc, -CH2NMeBoc, -CH2NH2, and -CH2NHMe). Cross-polarization magic angle spinning (13)C NMR spectra showed that CO2 binds chemically to IRMOF-74-III-CH2NH2 and -CH2NHMe to make carbamic species. Carbon dioxide isotherms and breakthrough experiments show that IRMOF-74-III-CH2NH2 is especially efficient at taking up CO2 (3.2 mmol of CO2 per gram at 800 Torr) and, more significantly, removing CO2 from wet nitrogen gas streams with breakthrough time of 610 ± 10 s g(-1) and full preservation of the IRMOF structure.

The design of enzyme-like complexity within metal–organic frameworks (MOFs) requires multiple reactions to be performed on a MOF crystal without losing access to its interior. Here, we show that seven post-synthetic reactions can be successfully achieved within the pores of a multivariate MOF, MTV-IRMOF-74-III, to covalently incorporate tripeptides that resemble the active sites of enzymes in their spatial arrangement and compositional heterogeneity. These reactions build up H2N-Pro-Gly-Ala-CONHL and H2N-Cys-His-Asp-CONHL (where L = organic struts) amino acid sequences by covalently attaching them to the organic struts in the MOFs, without losing porosity or crystallinity. An enabling feature of this chemistry is that the primary amine functionality (−CH2NHBoc) of the original MOF is more reactive than the commonly examined aromatic amines (−NH2), and this allowed for the multi-step reactions to be carried out in tandem within the MOF. Preliminary findings indicate that the complexity thus achieved can affect reactions that were previously accomplished only in the presence of enzymes.

Acenes are highly promising p-type organic semiconductors, and have been the subject of intense studies. However, acenes are often low in solubility and stability, which poses major obstacles in the synthesis and processing of this class of compounds. In order to overcome the problem, a series of diketone-type acene precursors have been developed. These precursors are generally more soluble and stable than the corresponding acene compounds, and their quantitative conversion can be achieved simply by photoirradiation both in solution and in the solid state. Further, the irreversible photoinduced removal of the -diketone unit can be used to alter the optoelectronic properties of fluorophores. This review overviews the synthesis and photochemical properties of -diketone-type acene precursors, as well as their use as intermediates in preparation of large acenes or highly functionalized acene derivatives. Computational studies on the mechanism of -diketone photolysis and the use of diketone derivatives in fabrication of organic devices are also summarized in this review.

Dehydro[24]annulene 1c adopts an unusual planarized conformation in the crystal. A multilayered stack of hydrogen-bonded grids delineates tightly packed nanotubular channels. The related macrocycles 1a and 1b, on the other hand, have the expected puckered conformations in the crystal.

The vertical composition profile of active layer has a major effect on the performance of organic photovoltaic devices (OPVs). While stepwise deposition of different materials is a conceptually straightforward method for controlled preparation of multi-component active layers, it is practically challenging for solution processes because of dissolution of the lower layer. Herein, we overcome this difficulty by employing the photoprecursor approach, in which a soluble photoprecursor is solution-deposited then photoconverted in situ to a poorly soluble organic semiconductor. This approach enables solution-processing of the p-i-n triple-layer architecture that has been suggested to be effective in obtaining efficient OPVs. We show that, when 2,6-dithienylanthracene and a fullerene derivative PC71BM are used as donor and acceptor, respectively, the best p-i-n OPV affords a higher photovoltaic efficiency than the corresponding p-n device by 24% and bulk-heterojunction device by 67%. The photoprecursor approach is also applied to preparation of three-component p-i-n films containing another donor 2,6-bis(5′-(2-ethylhexyl)-(2,2′-bithiophen)-5-yl)anthracene in the i-layer to provide a nearly doubled efficiency as compared to the original two-component p-i-n system. These results indicate that the present approach can serve as an effective means for controlled preparation of well-performing multi-component active layers in OPVs and related organic electronic devices.

Careful molecular engineering has enabled solution processing of well-performing bulk-heterojunction photovoltaic layers comprising insoluble materials.

Gold(I), silver(I), and copper(I) phosphine complexes of 6,9,12,15,18-pentaaryl[60]fullerides 1a and 1b, namely, [(4-MeC(6)H(4))(5)C(60)]Au(PPh(3)) (2a), [(4-t-BuC(6)H(4))(5)C(60)]Au(PPh(3)) (2b), [(4-MeC(6)H(4))(5)C(60)]Ag(PCy(3)) (3a), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PPh(3)) (3b), [(4-t-BuC(6)H(4))(5)C(60)]Ag(PCy(3)) (3c), [(4-MeC(6)H(4))(5)C(60)]Cu(PPh(3)) (4a), and [(4-t-BuC(6)H(4))(5)C(60)]Cu(PPh(3)) (4b), have been synthesized and characterized spectroscopically. All complexes except for 3c were also characterized by single-crystal X-ray diffraction. Several coordination modes between the cyclopentadienyl ring embedded in the fullerene and the metal centers are observed, ranging from η(1) with a slight distortion toward η(3) in the case of gold(I), to η(2)/η(3) for silver(I), and η(5) for copper(I). Silver complexes 3a and 3b are rare examples of crystallographically characterized Ag(I) cyclopentadienyls whose preparation was possible thanks to the steric shielding provided by fullerides 1a and 1b, which stabilizes these complexes. Silver complexes 3a and 3b both display unexpected coordination of the cyclopentadienyl portion of the fulleride anion with Ag(I). DFT calculations on the model systems (H(5)C(60))M(PH(3)) and CpMPH(3) (M = Au, Ag, or Cu) were carried out to probe the geometries and electronic structures of these metal complexes.

A new tetraazatetracene derivative, 2,3-[4,4'-bis(N,N-diphenylamino)benzyl]-5,12-bis[(triisopropylsilyl)ethynyl]-1,4,6,11-tetraazatetracene (TPAs-BTTT), displays rewritable multilevel memory behavior, which is probably induced by multielectron intramolecular charge transfer (CT).