New classes of nanoporous organic polymers based on 1,3,5-triazine units (NOP-1-6) were synthesized via a straightforward, methane-sulfonic acid-catalysed, cost-effective Friedel-Crafts reaction of 2,4,6trichloro-1,3,5-triazine and tetrahedral building blocks. Among them, NOP-3 with a Brunauer-Emmet-Teller (BET) specific surface area up to 894 m 2 g À1 and the total volume exceeding 0.41 m 3 g À1 exhibits good hydrogen adsorption capacity (up to 1.14 wt% at 77 K/1.0 bar) and high carbon dioxide uptake (up to 11.03 wt% at 273 K/1.0 bar). Furthermore, it presents an effective selectivity for CO 2 adsorption (NOP-6, CO 2 /N 2 selectivity 38.7 at 273 K/1.0 bar), demonstrating potential applications in gas adsorption and separation.

Two cationic iridium complexes, namely [Ir(dph-oxd)2(bpy)]PF6 (1) and [Ir(dph-oxd)2(pzpy)]PF6 (2), using 2,5-diphenyl-1,3,4-oxadiazole (dph-oxd) as the cyclometallating ligand and 2,2'-bipyridine (bpy) or 2-(1H-pyrazol-1-yl)pyridine (pzpy) as the ancillary ligands, have been synthesized, and their photophysical and electrochemical properties have been comprehensively investigated. In solution, both complexes emit efficient blue-green light. For complex 1, the light emission in a neat film is remarkably red-shifted; in solid state, it gives an intriguing piezochromic phenomenon. Compared with archetype [Ir(ppy)2(bpy)]PF6 (ppy is 2-phenylpyridine), complex 1 shows a largely stabilized HOMO (highest occupied molecular orbital) level, induced by the electron-deficient 1,3,4-oxadiazole (oxd) heterocycle of dph-oxd, which results in an enlarged energy gap and blue-shifted emission. Compared with complex 1, complex 2 shows an enhanced LUMO (lowest unoccupied molecular orbital) level, caused by the electron-rich pzpy ancillary ligand, but they exhibit similar emission energy in solution. For both complexes, theoretical calculations reveal that their blue-green emission in solution arises primarily from the (3)π-π* states centered on dph-oxd; moreover, complex 1 bears close-lying (3)π-π* and (3)CT (charge-transfer) states, underlying its remarkably red-shifted emission in the neat film and unique piezochromic behavior in the solid state. Solid state light emitting electrochemical cells (LECs) based on complexes 1 and 2 give efficient yellow and green-blue light, with peak current efficiencies of 18.3 and 5.2 cd A(-1), respectively. It is demonstrated that oxd-type cyclometallating ligands are promising as an avenue to stabilize the HOMOs and tune emission properties of cationic iridium complexes to a large extent.

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A route toward fluorine-free blue-emitting cationic iridium complexes, to generate emission from the cyclometalating ligands with enhanced triplet energy, has been proposed and demonstrated. Attaching electron-donating groups to the pyridine moieties of the ppy-type cyclometalating ligands (Hppy is 2-phenylpyridine) enhances the triplet ((3)π-π*) energy of the ligand, and the use of electron-rich or non-conjugated ancillary ligands ensures that the emission is generated from the (3)π-π* states of cyclometalating ligands. By this molecular design, [Ir(buoppy)2(pzpy)]PF6 (1) and [Ir(buoppy)2(bim-cb)]PF6 (2) have been developed, with 4-butoxy-2-phenylpyridine (buoppy) as the cyclometalating ligand and electron-rich 2-(1H-pyrazol-1-yl)pyridine (pzpy) or non-conjugated N-heterocyclic dicarbene (bim-cb) as the ancillary ligands. Complexes 1 and 2 give emission with major emission peaks around 465 nm, which is among the bluest reported for fluorine-free cationic iridium complexes. For both complexes, the emission is generated from the (3)π-π* states centered on buoppy. For complex 1, the charge-transfer (Ir/buoppy → pzpy) state is dominated by non-radiative deactivation and it behaves as a non-radiative deactivation channel for the emissive buoppy-centered (3)π-π* states which lies close to the charge-transfer state in energy. Such a non-radiative deactivation channel is largely suppressed in the rigid matrix, and is eliminated in complex 2 with a non-conjugated dicarbene ancillary ligand.

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