The self-assembly of a well-defined and astutely designed, low-molecular weight gelator (LMWG) based linker with a suitable metal ion is a promising method for preparing photocatalytically active coordination polymer gels. Here, we report the design, synthesis, and gelation behaviour of a tetrapodal LMWG based on a porphyrin core connected to four terpyridine units (TPY-POR) through amide linkages. The self-assembly of TPY-POR LMWG with Ru II ions results in a Ru-TPY-POR coordination polymer gel (CPG), with a nanoscroll morphology. Ru-TPY-POR CPG exhibits efficient CO 2 photoreduction to CO (3.5 mmol g À 1 h À 1 ) with > 99 % selectivity in the presence of triethylamine (TEA) as a sacrificial electron donor. Interestingly, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH) with TEA as the sacrificial electron donor, the 8e À /8H + photoreduction of CO 2 to CH 4 is realized with > 95 % selectivity (6.7 mmol g À 1 h À 1 ). In CPG, porphyrin acts as a photosensitizer and covalently attached [Ru(TPY) 2 ] 2 + acts as a catalytic center as demonstrated by femtosecond transient absorption (TA) spectroscopy. Further, combining information from the in situ DRIFT spectroscopy and DFT calculation, a possible reaction mechanism for CO 2 reduction to CO and CH 4 was outlined.

The much-needed renewable alternatives to fossil fuel can be achieved efficiently and sustainably by converting solar energy to fuels via hydrogen generation from water or CO2 reduction. Herein, a soft processable metal-organic hybrid material is developed and studied for photocatalytic activity towards H2 production and CO2 reduction to CO and CH4 under visible light as well as direct sunlight irradiation. A tetrapodal low molecular weight gelator (LMWG) is synthesized by integrating tetrathiafulvalene (TTF) and terpyridine (TPY) derivatives through amide linkages and results in TPY-TTF LMWG. The TPY-TTF LMWG acts as a linker, and self-assembly of this gelator molecules with ZnII ions results in a coordination polymer gel (CPG); Zn-TPY-TTF. The Zn-TPY-TTF CPG shows high photocatalytic activity towards H2 production (530 μmol g−1h−1) and CO2 reduction to CO (438 μmol g−1h−1, selectivity > 99%) regulated by charge-transfer interactions. Furthermore, in situ stabilization of Pt nanoparticles on CPG (Pt@Zn-TPY-TTF) enhances H2 evolution (14727 μmol g−1h−1). Importantly, Pt@Zn-TPY-TTF CPG produces CH4 (292 μmol g−1h−1, selectivity > 97%) as CO2 reduction product instead of CO. The real-time CO2 reduction reaction is monitored by in situ DRIFT study, and the plausible mechanism is derived computationally.

Bandgap engineering in donor–acceptor conjugated microporous polymers (CMPs) is a potential way to increase the solar‐energy harvesting towards photochemical water splitting. Here, the design and synthesis of a series of donor–acceptor CMPs [tetraphenylethylene (TPE) and 9‐fluorenone (F) as the donor and the acceptor, respectively], F0.1CMP, F0.5CMP, and F2.0CMP, are reported. These CMPs exhibited tunable bandgaps and photocatalytic hydrogen evolution from water. The donor–acceptor CMPs exhibited also intramolecular charge‐transfer (ICT) absorption in the visible region (λmax=480 nm) and their bandgap was finely tuned from 2.8 to 2.1 eV by increasing the 9‐fluorenone content. Interestingly, they also showed emissions in the 540–580 nm range assisted by the energy transfer from the other TPE segments (not involved in charge‐transfer interactions), as evidenced from fluorescence lifetime decay analysis. By increasing the 9‐fluorenone content the emission color of the polymer was also tuned from green to red. Photocatalytic activities of the donor–acceptor CMPs (F0.1CMP, F0.5CMP, and F2.0CMP) are greatly enhanced compared to the 9‐fluorenone free polymer (F0.0CMP), which is essentially due to improved visible‐light absorption and low bandgap of donor–acceptor CMPs. Among all the polymers F0.5CMP with an optimum bandgap (2.3 eV) showed the highest H2 evolution under visible‐light irradiation. Moreover, all polymers showed excellent dispersibility in organic solvents and easy coated on the solid substrates.

A lanthanide based photochromic coordination polymer gel (pcCPG) material has been developed which showed photomodulated colour change based on pcFRET and has the potential to be employed for decoding secret information.

Synthesis and stabilization of ultra-small metal nanoparticles (MNPs) composed of few atoms are of paramount importance in modulating their material properties based on quantum confinement effects. The highly reactive surface...

Colocalization of essential molecular components in the solvated soft supramolecular assembly towards realizing visible-light-driven hydrogen evolution would be an exciting approach for sustainable energy by generating clean solar fuel. In...

Design and synthesis of solid-state photochromic materials remain a challenge because of high structural constrain. However, this can be mitigated in attaining structural flexibility by introducing permanent porosity into the system. Here, we report for the first time the design and synthesis of a photochromic conjugated microporous polymer (pcCMP) by assembling photochromic dithienylethene aldehyde and benzene-1,3,5-tricarbohydrazide. The yellow photo-isomer pcCMP-O gets converted to a deep-green photo-isomer pcCMP-C by UV-light irradiation, which can be reverted to pcCMP-O by visible light or thermal treatment. Owing to the thermo-irreversible nature, the pcCMP is found to be suitable for designing an INH functioning logic gate. pcCMP-C shows highly enhanced conductivity (92 times) because of enhanced conjugation compared to pcCMP-O. Furthermore, we demonstrate the bio-inspired photo-switchable pcFRET process by encapsulation of a red-emissive green fluorescent protein (gfp) chromophore analogue into the pcCMP. This material shows high processibility and has been exploited further for secret writing.

A new π-chromophoric and asymmetric bola-amphiphilic oligo-( p-phenylene ethynylene)-based tetracarboxylate (OPE-TC1) linker was designed, synthesized, and self-assembled with Zn(OAc). The resulting nanoscale metal-organic framework (MOF) {Zn(OPE-TC1)} (NMOF-1) showed a vesicular morphology and permanent porosity with omniphilic pore surface. NMOF-1 showed cyan emission with high quantum efficiency (49%). The omniphilicity of the pore was utilized to incorporate ambipolar dye sulforhodamine G (SRG) to tune the band gap as well as to get pure white-light emission. Furthermore, the polar pore surface of NMOF-1 allowed facile diffusion of the substrate for efficient photocatalytic activity. The dye-encapsulated framework further showed enhanced dihydrogen production by 1.75-fold compared to that from the as-synthesized NMOF-1 because of the modulated band gap and high excited state lifetime. As a control experiment, we have synthesized a MOF (MOF-OMe) with an OPE-TC2 linker having -OMe functional groups that did not show nanoscale architecture. This suggested the important role of unsymmetrical bola-amphiphilicity in nanostructuring. This rational design of a chromophoric linker resulted in a nanoscale MOF with omniphilic porosity to achieve bimodal functionality in clean energy applications.