{'fraction_non_alphanumeric': 0.05101535413571075, 'fraction_numerical': 0.03665180782565627, 'mean_word_length': 5.082831325301205, 'pattern_counts': {'":': 0, '<': 0, '<?xml version=': 0, '>': 1, 'https://': 0, 'lorem ipsum': 0, 'www.': 0, 'xml': 0}, 'pii_count': 0, 'substrings_counts': 0, 'word_list_counts': {'cursed_substrings.json': 0, 'profanity_word_list.json': 0, 'sexual_word_list.json': 0, 'zh_pornsignals.json': 0}}
Regioselective Functionalization of the Mesoporous Metal–Organic Framework, NU-1000, with Photo-Active Tris-(2,2′-bipyridine)ruthenium(II)

Solvent-assisted ligand incorporation is an excellent method for the post-synthetic functionalization of Zr-based metal–organic frameworks (MOFs), as carboxylate-derivative functionalities readily coordinate to the Zr6 nodes by displacing node-based aqua and terminal hydroxo ligands. In this study, a photocatalytically active ruthenium complex RuII(bpy)2(dcbpy), that is, bis-(2,2′-bipyridine)-(4,4′-dicarboxy-2,2′-bipyridine)ruthenium, was installed in the mono-protonated (carboxylic acid) form within NU-1000 via SALI. Crystallographic information regarding the siting of the ruthenium complex within the MOF pores is obtained by difference envelope density analysis. The ruthenium-functionalized MOF, termed Ru-NU-1000, shows excellent heterogeneous photocatalytic activity for an oxidative amine coupling reaction.


Section S2. Difference envelope density (DED) analysis
Ambient temperature powder diffraction data were collected at beamline 17-BM-B at the Advanced Photon Source using 17.04 keV (0.72768 Å) x-rays. Capillaries were loaded with powdered samples, then placed into a sample changer cassette.
Diffraction patterns were collected using an amorphous silicon area detector. Calibration and data reduction to one-dimensional patterns were performed using GSAS-II. [1] Lattice parameters were extracted from powder diffraction patterns via Le Bail whole pattern fitting. [2,3] A previously published crystal structure for NU-1000 (P6/mmm) was used as a starting model for these analyses. [4] Hexagonal lattice and pseudo-Voigt profile parameters were refined. Structure envelopes were generated from the extracted intensities of 24 reflections (out to {6 -1 0}) using previously described methods. [3,[5][6][7] Difference envelope densities were then calculated via subtraction of the structure envelope of NU-1000 from that of Ru-NU-1000 to approximate the location of electron density associated with Ru. [8] Surfaces were drawn at >1.7σ level to preferentially show contributions from Ru.
Section S3. Photocatalytic reaction [9,10] To demonstrate the photocatalytic ability of Ru-NU-1000, an amino oxidative coupling was performed. 3 mg of Ru-NU-1000 (the amount of Ru complex was calculated based on the ratio of Zr 6 node and Ru complex in Ru-NU-1000 by ICP-OES) were dispersed in 1 ml toluene and 100 mol equivalent 4-methylbenzylamine against Ru complex were also added as a substrate. Then, the dispersion was sealed in a microwave glass tube, and the dispersion was purged with O 2 for 1 minute. Then, the dispersion was irradiated with Blue LED (450 nm). After irradiation, the dispersion was filtered to remove insoluble contents. The filtrate was dried once under reduced pressure and re-dissolved in deuterochloroform for 1 H-NMR measurement. The conversion yield for amine oxidative coupling of 4-methylbenzylamine was calculated by comparing integration ratio between the peak of substrate and product (Conversion yield = 2*Product / (Substrate + 2*Product)) ( Fig. S4).
For the reuse experiment, once used Ru-NU-1000 was washed with acetonitrile several times and then used for a new photocatalytic reaction. Furthermore, the structure preservation of once used Ru-NU-1000 was confirmed PXRD measurement (Fig. S5).
As control experiments, the photocatalytic reaction was carried out with 1 mol% [Ru(bpy) 2 (dcbpy)](PF 6 ) 2 in acetonitrile and bare NU-1000 in toluene under the same condition. The amount of NU-1000 was calculated by subtracting the amount of Ru complex from 3 mg of Ru-NU-1000 Figure S4. 1 H-NMR spectra of each photocatalysis condition. The peaks around 3.8 ppm and 4.76 ppm were assigned to substrate and product, respectively. Figure S5. PXRD patterns of Ru-NU-1000 once used for photocatalysis (red) and unused Ru-NU-1000 (green) Figure S6. The diffuse reflectance UV spectra (left) and steady state emission spectra of NU-1000 and Ru-NU-1000.