Photodynamic therapy (PDT) uses photosensitizers (PS) which only become cytotoxic upon light‐irradiation. Transition‐metal complexes are highly promising PS due to long excited‐state lifetimes, and high photo‐stabilities. However, these complexes usually absorb higher‐energy UV/Vis light, whereas the optimal tissue transparency is in the lower‐energy NIR region. Two‐photon excitation (TPE) can overcome this dichotomy, with simultaneous absorption of two lower‐energy NIR‐photons populating the same PS‐active excited state as one higher‐energy photon. We introduce two low‐molecular weight, long‐lived and photo‐stable iridium complexes of the [Ir(N^C)2(N^N)]+ family with high TP‐absorption, which localise to mitochondria and lysosomal structures in live cells. The compounds are efficient PS under 1‐photon irradiation (405 nm) resulting in apoptotic cell death in diverse cancer cell lines at low light doses (3.6 J cm−2), low concentrations, and photo‐indexes greater than 555. Remarkably 1 also displays high PS activity killing cancer cells under NIR two‐photon excitation (760 nm), which along with its photo‐stability indicates potential future clinical application.

3 Shaping of metal-organic frameworks (MOFs) has become increasingly studied over the past few 4 years because it represents a major bottleneck toward their further applications at larger scale. 5 MOF-based macroscale solids should present similar performances to their powder counterparts along with adequate mechanical resistance. 3D printing is one of the promising technologies as it 7 allows the fast prototyping of materials at the macroscale; however, the large amounts of added 8 binders have a detrimental effect on the porous properties of the solids. Herein, a 3D printer was 9 modified to prepare a variety of MOF-based solids with controlled morphology from shear-10 thinning inks containing 2-hydroxyethyl cellulose. Four benchmark MOFs were tested for this 11 purpose: HKUST-1, CPL-1, ZIF-8 and UiO-66-NH 2. All solids are mechanically stable up to 0.6 12 MPa of uniaxial compression and highly porous with BET specific surface areas lowered by 0 to 13-25%. Furthermore, these solids were applied to high pressure hydrocarbon sorption (CH 4 , C 2 H 4 14 and C 2 H 6) and presented consequent methane gravimetric uptake (UiO-66-NH 2 , ZIF-8, and 15 HKUST-1) and highly preferential adsorption of ethylene of ethane (CPL-1).