Over the past two decades, supramolecular gels have attracted significant attention from scientists in diverse research fields and have been extensively developed. This review mainly focuses on the significant achievements in supramolecular gels and catalysis. First, by incorporating diverse catalytic sites and active organic functional groups into gelator molecules, supramolecular gels have been considered as a novel matrix for catalysis. In addition, these rationally designed supramolecular gels also provide a variety of templates to access metal nanocomposites, which may function as catalysts and exhibit high activity in diverse catalytic transformations. Finally, as a new kind of biomaterial, supramolecular gels formed in situ by self-assembly triggered by catalytic transformations are also covered herein.

The option of conjugated π-linkers is critical for molecular engineering toward the energy-level strategy of donor−π–acceptor (D−π–A) sensitizers. There is always a balance in the optimization of a π-linker. The π-conjugation should be enlarged to expand the light-harvesting capability of sensitizers for an increase in photocurrent; however, the oversized π-linker also would affect seriously the photovoltage and photostability. Two sensitizers, WS-22 and WS-23, are constructed without or with benzothiadiazole (BTD) in a molecular skeleton, aiming to gain insight into the effect of an auxiliary acceptor in D–A−π–A sensitizers on the photophysical and photovoltaic performances, especially focusing on the exploitation of the short circuit current density (J sc) and open circuit voltage (V oc). Compared with the typical D−π–A sensitizer WS-22, the incorporation of an auxiliary acceptor of BTD in WS-23 can improve the light-harvesting ability both in red-shifting the absorption peaks and the increment of absorption coefficient. The predominant increase by 15.6% in light-harvesting efficiency (LHE) of WS-23 results in a relatively higher J sc from 13.77 (WS-22) to 16.91 mA cm–2 (WS-23). Moreover, the improvement of the V oc in WS-23 is originated by a synergy contribution of the uplifting of E CB and inhibition of charge recombination. The stepped light-induced transient (SLIT) measurements indicate that the introduction of BTD can negatively shift the conduction band of the TiO2 film. For WS-23, the higher molecular dipole moment can bring forth a more effective charge separation between donor and acceptor units, also resulting in an increase in V oc. The incorporated BTD unit can increase V oc by 57 mV, arising from the CB edge shift of TiO2 (accounting for 40%, 23 mV) and the retarding charge recombination (accounting for 60%, 34 mV). As a consequence, WS-23 realizes an optimizing photovoltaic efficiency (η = 8.15%), with an improvement of 36.5% with respect to WS-22.

A single-step gold­(I)-catalyzed chemoselective protocol to access ortho-substituted diarylsulfones has been established. Acenaphthoimidazolylidene gold complexes are effective catalysts for the arylsulfonylation of boronic acids by potassium metabisulfite (K2S2O5) and diaryliodonium salts to access (poly-)ortho-substituted diarylsulfones even in gram scale. Unlike the transition metal-catalyzed two-component coupling systems, the sterically hindered aryl groups in diaryliodonium salts are preferentially transferred over less bulky ones to form synthetically difficult targets, including those of pharmaceutical importance.

Lowering the LUMOs and decreasing energy “waste” is targeted through inserting an auxiliary group from an electron donor or acceptor into D–π–A organic sensitizers, and the photovoltaic efficiency increases 38 fold from 0.24 to 9.46%.

supported catalysts by simply knitting rigid aromatic ligands via hypercross-linking (Friedel-Crafts reactions) has recently been proposed. [13] After further postmodification/activation, several MCPPs have been successfully developed. [14][15][16][17] However, with postmodification, avoiding the problems, like low density of catalytic sites due to incomplete modification and random/ nonselective metal anchoring, can be difficult. These issues may still lead to low catalytic activity and selectivity, especially in some challenging transformations. [18] In light of N-heterocyclic carbene-metal (NHC-M) complexes can act as robust and viable catalysts in a broad range of reactions, [19][20][21][22][23][24][25][26][27][28] various strategies have been developed for their immobilization. [29,30] Among them, selfsupporting strategy may represent one of the most practical and efficient approaches. [31][32][33][34] It has to be noted that NHC ligands still have to be carefully designed and modified before selfsupporting. Alternatively, the high catalytic activities and robustness of NHC-M complexes make them perfect candidates for direct knitting. To the best of our knowledge, there are only two reported examples on MCPPs in which the NHC ligands are firstly knitted and then coordinated to active metal ions (postmodification approach). [14,15] Direct knitting of NHC-M complexes to fabricate porous organometallic polymers (POMPs) that do not require postmodification/activation is still unknown.Herein, we have designed and prepared a series of unprecedented porous organometallic polymers POMPs-NHC-M 1-3 via direct knitting three types of bis-chelating NHC-M complexes (M = Ir, Pd, and Ru, Figure 1a). Using this facile strategy, which does not require postmodification/activation, 1) the metal active sites are atomically dispersed in the hierarchical porous matrix, and 2) the intrinsic well-defined bis-chelating mode and their molecular catalytic properties are maximally retained, which allows 3) the precise design and control of the immobilized catalysts at the molecular level. The advantages of direct knitting allow the resulting POMPs-NHC-M 1-3 to behave as recyclable solid single-site catalysts and exhibit extremely high catalytic activities in both hydrogenation and dehydrogenation reactions.In light of their robustness toward Friedel-Crafts reaction conditions, bis-chelating NHC-M (Ir, Pd and Ru) complexes 4, 5 and 6, derived from corresponding benzimidazolium salts, [24,25,27] were selected to fabricate POMPs via direct knitting with benzene ( Figure 1a). Concerning the plausible impact Porous organometallic polymers (POMPs) with hierarchical pore structures, high specific surface areas, and atomically dispersed metal (Ir, Pd, Ru) centers are successfully fabricated by a facile one-pot method through direct knitting of diverse N-heterocyclic carbene metal (NHC-M) complexes. These polymers can function as recyclable solid single-site catalysts and exhibit excellent catalytic activity and selectivity in both dehydrogenat...

Indoline-based D-A-π-A organic sensitizers are promising candidates for highly efficient and long-term stable dye-sensitized solar cells (DSSCs). In order to further broaden the spectral response of the known indoline dye WS-2, we rationally engineer the molecular structure through enhancing the electron donor and extending the π-bridge, resulting in two novel indoline-based D-A-π-A organic sensitizers WS-92 and WS-95. By replacing the 4-methylphenyl group on the indoline donor of WS-2 with a more electron-rich carbazole unit, the intramolecular charge transfer (ICT) absorption band of dye WS-92 is slightly red-shifted from 550 nm (WS-2) to 554 nm (WS-92). In comparison, the incorporation of a larger π-bridge of cyclopentadithiophene (CPDT) unit in dye WS-95 not only greatly bathochromatically tunes the absorption band to 574 nm but also largely enhances the molar extinction coefficients (ε), thus dramatically improving the light-harvesting capability. Under the standard global AM 1.5 solar light condition, the photovoltaic performances of both organic dyes have been evaluated in DSSCs on the basis of the iodide/triiodide electrolyte without any coadsorbent or cosensitizer. The DSSCs based on WS-95 display better device performance with power conversion efficiency (η) of 7.69%. The additional coadsorbent in the dye bath of WS-95 does not improve the photovoltaic performance, indicative of its negligible dye aggregation, which can be rationalized by the grafted dioctyl chains on the CPDT unit. The cosensitization of WS-95 with a short absorption wavelength dye S2 enhances the IPCE and improves the η to 9.18%. Our results indicate that extending the π-spacer is more rational than enhancing the electron donor in terms of broadening the spectral response of indoline-based D-A-π-A organic sensitizers.

A robust acenaphthoimidazolylidene gold complex is demonstrated as a highly efficient catalyst in the direct alkylsulfonylation of boronic acids. Remarkably, a wide range of highly reactive and unreactive C-electrophiles were well-tolerated to produce various (hetero)­aryl-alkyl, aryl-alkenyl, and alkenyl-alkyl sulfones in satisfactory yields with 5 mol % catalyst loading. Along with the steric properties of NHC ligands, the high catalytic activity of this gold complex suggests that the strong σ-donation of acenaphthoimidazolylidene also played a role in promoting this challenging redox-neutral catalytic process.

Robust N-heterocyclic carbene palladium complexes are highly efficient catalysts for direct alkylsulfonylation of (hetero)aryl- or alkenyl-boronic acids with potassium metabisulfite and (hetero)alkyl-halides. Among them, acenaphthoimidazolylidene palladium(ii) complexes exhibited the highest activities, and up to quantitative yields were obtained for diverse structurally distinct sulfones under very mild reaction conditions.