CC BY-NC-ND 4.0Tholen, PatrikPatrikTholenPeeples, CraigCraigPeeplesAyhan, Mehmet M.Mehmet M.AyhanWagner, LukasLukasWagnerThomas, HeidiHeidiThomasImbrasas, PauliusPauliusImbrasasZorlu, YunusYunusZorluBaretzky, ClemensClemensBaretzkyReineke, SebastianSebastianReinekeHanna, GabrielGabrielHannaYücesana, GündoğGündoğYücesana2023-03-132023-03-132022Note-ID: 000094F2https://publica.fraunhofer.de/handle/publica/437581https://doi.org/10.24406/publica-103310.1002/smll.20220457810.24406/publica-1033Herein, a simple way of tuning the optical and structural properties of porphyrin-based hydrogen-bonded organic frameworks (HOFs) is reported. By inserting transition metal ions into the porphyrin cores of GTUB-5 (p-H8-TPPA (5,10,15,20-Tetrakis[p-phenylphosphonic acid] HOF), the authors show that it is possible to generate HOFs with different band gaps, photoluminescence (PL) life times, and textural properties. The band gaps of the resulting HOFs (viz., Cu-, Ni-, Pd-, and Zn-GTUB-5) are measured by diffuse reflectance and PL spectroscopy, as well as calculated via DFT, and the PL lifetimes are measured. Across the series, the band gaps vary over a narrow range from 1.37 to 1.62 eV, while the PL lifetimes vary over a wide range from 2.3 to 83 ns. These differences ultimately arise from metal-induced structural changes, viz., changes in the metal-to-nitrogen distances, number of hydrogen bonds, and pore volumes. DFT reveals that the band gaps of Cu-, Zn-, and Pd- GTUB-5 are governed by highest occupied/lowest unoccupied crystal orbitals (HOCO/LUCO) composed of π- orbitals on the porphyrin linkers, while that of Ni-GTUB-5 is governed by a HOCO and LUCO composed of Ni dorbitals. Overall, our findings show that metal-insertion can be used to optimize HOFs for optoelectronics and small-molecule capture applications.endensity functional theory calculationshydrogen-bonded organic frameworksmofphotoluminescencephotoluminescence imagingPhotovoltaikPerowskit- und Organische PhotovoltaikPerowskitsolarzellen und -modulejournal article