Photoresponsive proton conduction in Zr-based metal–organic frameworks using the photothermal effect

Qin, Ming-Feng; Wang, Changyu; Bao, Song‐Song; Zheng, Li‐Min

doi:10.1039/d2cc02470e

Cited by 14 publications

(11 citation statements)

References 41 publications

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“…It is worth mentioning that porphyrin-phosphonate-based MOFs or CPs are still limited in number. They usually contain only one kind of ligand such as M–H 8 TPPP (M = Ni, Cu) or H 10 TPPP and show 3D framework structures. ,,, The only exception, as far as we are aware, is [(CH 3 ) 2 NH 2 ] 2 [Ni(Cu–H 4 TPPP)] which has a 1D chain structure . Thus, compounds CoNi , NiNi , and CoCo are the second examples of metal porphyrin-tetraphosphonates showing a 1D chain structure.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we found that the absorption bands of a highly stable 3D Zr-MOF based on 5,10,15,20-tetrakis( p -phenylphosphonic acid)-porphyrin (H 10 TPPP) approached ca. 1200 nm in the solid state . The significant red-shift of the absorption band is attributed to the rigid framework structure and the π–π interactions between the stacked porphyrin moieties in the structure .…”

Section: Introductionmentioning

confidence: 93%

“…1200 nm in the solid state. 25 The significant redshift of the absorption band is attributed to the rigid framework structure and the π−π interactions between the stacked porphyrin moieties in the structure. 26 We hypothesize that not only 3D porphyrin-phosphonate MOFs but also 1D CPs containing stacked porphyrin rings can show absorption bands red-shifted to the NIR region.…”

Section: ■ Introductionmentioning

confidence: 99%

“…They usually contain only one kind of ligand such as M−H 8 TPPP (M = Ni, Cu) or H 10 TPPP and show 3D framework structures. 25,27,28,30 Chemical Stability and Exfoliating in Water. Compounds CoNi, NiNi, and CoCo are stable in common organic solvents such as methanol (CH 3 OH), chloroform (CHCl 3 ), tetrahydrofuran (THF), acetone, and acetonitrile (CH 3 CN), as confirmed by the powder X-ray diffraction (PXRD) measurements (Figures S7−S9).…”

Section: ■ Introductionmentioning

confidence: 99%

“…1500 nm, unlike most of the other porphyrin-based MOFs or CPs which absorbed light below 750 nm 21,22 and also a zirconium porphyrin-phosphonate which absorbed light below 1200 nm. 25 The significant bathochromic-shift of absorption in Ni− H 8 TPPP, CoNi, NiNi, and CoCo is ascribed to the formation of rigid supramolecular frameworks, the π−π interactions between the stacked porphyrin rings, and possible charge transfer from a phosphonate oxygen donor to the porphyrin/phen acceptor within the chain. We also investigated the UV−vis−NIR absorption spectra of Ni−H 8 TPPP (25 μg/mL), CoNi-n, NiNi-n, and CoCo-n in HEPES solution (50 μg/mL) at pH = 7.4.…”

Section: ■ Introductionmentioning

confidence: 99%

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Metalloporphyrinyl-Phosphonates with Serrated Chain Structures: Exfoliation and NIR Photothermal Effect

Qin

Zheng

Bao

et al. 2023

ACS Appl. Electron. Mater.

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Near-infrared (NIR) photothermal materials have received significant attention due to their potential applications in photothermal therapy, diagnosis, and imaging. In this work, we constructed three mixed-ligand metal phosphonates, namely, Co(Ni–H6TPPP)(phen)(H2O)2 (CoNi), Ni(Ni–H6TPPP)(phen)(H2O)2 (NiNi), and Co(Co–H6TPPP)(phen)(H2O)2 (CoCo), where H10TPPP is 5,10,15,20-tetrakis(p-phenylphosphonic acid)-porphyrin and phen is 1,10-phenanthroline. These compounds are isostructural showing 1D serrated chain structures in which the porphyrin rings are stacked between the chains with π–π interactions. All displayed a broad absorption from the UV–vis to NIR (ca. 1500 nm) regions in the solid state. Interestingly, the chains in these compounds can be chemically exfoliated in water by adjusting the pH, forming interwoven nanostrands/nanosheets with thicknesses of one to several chains. The photothermal effect was observed for CoNi, NiNi, and CoCo in the solid state and in HEPES solution (pH = 7.4) upon 808 nm laser irradiation, among which CoCo showed the highest photothermal conversion efficiency. The important role of the cobalt(II) ion in the porphyrin ring and phenylphosphonic unit in extending π-electron delocalization and enhancing the absorption in the NIR region in CoCo is revealed by theoretical calculations.

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