A series of porous organic polymers (POPs) were fabricated based on the boron dipyrromethene (BODIPY) core. The variation of the substituents in the BODIPY core and the fine tuning of the Sonogashira polycondenzation reaction with 1,3,5-triethynylbenzene led to the formation of POPs with a wide range of surface area and porosity. A tenfold increase in surface area from 73 m2g-1 in BDT1a polymer to 1010 m2g-1 in BDT3 was obtained. Simultaneously, the porosity was changed from mesoporous to ultramicroporous. The surface area of BDT3 turned out to be the highest reported so far for BODIPY based POPs. Molecular dynamics simulation coupled with Grand Canonical Monte Carlo simulations revealed the effect of substituents alkyl groups and rigidity of the core structures on the surface properties of the POPs. Detailed gas adsorption studies of the polymers revealed a high uptake of CO2 and H¬2. The highest uptake capacity of 16.5 wt. % for CO2 at 273 K and 2.2 wt.% for H¬2 at 77 K was observed for BDT3 at 1 bar pressure. Isosteric heat of adsorption (Qst) of BDT3 for CO2 was found to be as high as 30.6 kJ mol-1. Electron paramagnetic resonance studies revealed the generation of singlet oxygen upon photoexcitation of these polymers. The BODIPY based POPs turned out to be excellent catalysts for visible-light-driven photooxidation of thioanisole. The present study establishes BODIPY based POPs as a new class of multifunctional materials.

Fax: +91 (0)755 409 2392; Tel: +91 (0)755 669 2378. †Electronic Supplementary Information (ESI) available: [Details of characterizations of the polymer, molecular structures of the analytes, limits of detection, solid-state contact mode detection of nitroanilines, EPR and computational investigations.]. SeeA solution processable conjugated porous organic polymer (POP) based on tetraphenyl-5,5dioctylcyclopentadiene (TPDC-DB) was employed for nitroaromatics sensing by amplified fluorescence quenching. A comprehensive investigation was carried out using a set of 30 closely related analytes such as nitrophenols, nitrotoluenes, nitroanilines, nitobenzenes, quinones etc. Nitroanilines were found to be the most efficient quenchers in contrast to the extensively studied picric acid, which is unprecedented among POPs. Rigorous spectroscopic investigations including UV-Vis absorption, steady-state and time-resolved fluorescence, electron paramagnetic resonance coupled with computational studies provided new insight into the underlying photophysical phenomenon of fluorescence quenching. The Stern-Volmer plots were analyzed employing sphere of action model. It was observed that the electron-deficient nature of the nitroaromatics is not the sole governing factor responsible for fluorescence quenching. Naked eye detection of nitroanilines by TPDC-DB was also demonstrated. Detection limits for p-nitroaniline were found to be extremely low, 455 ppb in solution and ~ 1.8 ng cm -2 in contact mode. Scheme 1. Fabrication of porous organic polymer TPDC-DB by Sonogashira cross coupling between tetrakis(4-bromophenyl)-5,5dioctylcyclopentadiene and 1,4-diethynylbenzene.

Controlling the nonradiative deactivation of triplet states and tuning the singlet-triplet energy gap are the major challenges to develop materials exhibiting thermally activated delayed fluorescence (TADF) and room temperature phosphorescence...

The uniformly distributed nanoporous architectures in graphynes have significantly expanded the applicability of the materials of carbon flatland in areas such as water desalination, gas separation, energy storage, catalysis and optoelectronics.