A potential Cu/V-organophosphonate platform for tailored void spaces<i>via</i>terpyridine mold casting

Bulut, Aysun; Wörle, Michael; Zorlu, Yunus; Kirpi, Erdoğan; Zubieta, Jon; Grabowsky, Simon; Beckmann, Jens; Yücesan, Gündoğ

doi:10.1107/s2052520617000245

Cited by 16 publications

(11 citation statements)

References 66 publications

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“…Note that palladiumcatalyzed phosphonylation was previously achieved using the unusual Pd(PPh 3 ) 4 -triisopropyl phosphite system, at 220°C. 17,67 HRMS ( Fig. S9 and S10, ESI, † respectively.…”

Section: Methodsmentioning

confidence: 99%

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in O_h, T_d-cobalt(ii) tetraphenylmethane-based coordination polymers

et al. 2017

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The reaction of a phosphonate-diester tetraphenylmethane-based tecton, tetrakis[4-(diethoxyphosphoryl)phenyl]methane, (L) with cobalt(ii) chloride afforded a centrosymmetric coordination polymer (CP), [L·2Co(HO)·2CoCl], 2-Cl, possessing simultaneously octahedral (O) and tetrahedral (T) metal centers. This material served as a model compound for the demonstration of factors influencing the spectral dependence of one of the nonlinear optical (NLO) phenomena, the third-harmonic generation (THG). The spectrally-resolved THG (SR-THG) measurements in the range from 1125 to 1750 nm revealed that a maximum of THG response is obtained when the fundamental beam is around 1300 nm. The SR-THG study was combined with an analysis of the self-absorption effects of pumping and of third-harmonic radiation; based on these results, we put forward a hypothesis that the THG action spectrum is influenced more by the ability of the material to self-absorb the third harmonic rather than by the extent of self-absorption of the pumping radiation. Apart from investigations of NLO properties, we have explored coordination and particularly the supramolecular interactions that build up the 2-Cl CP. Despite the tetrahedral, spatial shape of the ligand L, CP 2-Cl has a two-dimensional net. The structure was found to be strongly supported by O-HCl hydrogen bonds, since each CoCl complex anion is an acceptor of eight of such interactions within a distorted square grid layer of cobalt(ii) ions. While coordination and hydrogen-bonded nets are both featuring the sql topology when treated separately, the consideration of both of them as topological paths yields a trinodal 4,4,6-connected net, described by the point symbol (4·8)(4·6)(4·6·8). SR-THG and structural studies of 2-Cl have been also supported by far- and mid-infrared spectroscopy, UV-Vis-NIR solid state absorption analysis, thermogravimetry and preliminary magnetic characterization.

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Section: Methodsmentioning

confidence: 99%

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in O_h, T_d-cobalt(ii) tetraphenylmethane-based coordination polymers

et al. 2017

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“…Due to the rich metal-binding modes of arylphosphonic acids, M-O-M condensations result in unpredictable oligomerizations of metal-phosphonate polyhedra in one, two, and even in three dimensions. [48,49] Therefore, to achieve predictable synthesis in metal phosphonate chemistry, it is important to restrain the metal-binding modes of phosphonic acids. Many different strategies have been employed to restrain their metal-binding modes such as using phosphonate monoesters and phosphinates.…”

Section: Synthesis Of Gtub3mentioning

confidence: 99%

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

Zorlu

Wagner

Tholen

et al. 2022

Advanced Optical Materials

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as paddle wheel patterns. [6,7] The ligandbinding modes around such molecular IBUs form large angles, ensuring separation between the organic struts and, in turn, resulting in large void spaces. [11] On the other hand, such separation limits the electrostatic interactions between the organic linkers. Therefore, traditional MOFs lack the required electron hopping and extended conjugation mechanisms between the bridging ligands to support electron mobility. [12][13][14] Although high surface area MOFs are ideal platforms to host electrons for supercapacitor applications, due to the lack of such mechanisms, conventional arylcarboxylate MOFs are generally known to be insulators. In addition to electrically conductive MOFs, photoluminescent MOFs have been the subject of active research due to their applications in sensing and light emitting diodes (LEDs). [15][16][17][18][19] In most cases, the photoluminescence is achieved either by the use of photoluminescent metal ions such as lanthanides, addition of fluorescent dyes to the MOF pores, or ligand exchange. [17,20] On the other hand, the photoluminescence in MOFs originating purely from the organic moieties is extremely rare and, to the best of our knowledge, there are no electrically conductive MOFs with high photoluminescence in the literature.Two-dimensional π-stacked MOFs based on ortho-diimine, ortho-dihydroxy, azolate, and thiolate metal-binding groups Herein, the design and synthesis of a highly photoluminescent and electrically conductive metal-organic framework [Zn{Cu-p-H 6 TPPA}]⋅2 [(CH 3 ) 2 NH](designated as GTUB3), which is constructed using the 5,10,15,20-tetrakis [p-phenylphosphonic acid] porphyrin (p-H 8 TPPA) organic linker, is reported. The bandgap of GTUB3 is measured to be 1.45 and 1.48 eV using diffuse reflectance spectroscopy and photoluminescence (PL) spectroscopy, respectively. The PL decay measurement yields a charge carrier lifetime of 40.6 ns. Impedance and DC measurements yield average electrical conductivities of 0.03 and 4 S m −1 , respectively, making GTUB3 a rare example of an electrically conductive 3D metal-organic framework. Thermogravimetric analysis reveals that the organic components of GTUB3 are stable up to 400 °C. Finally, its specific surface area and pore volume are calculated to be 622 m 2 g −1 and 0.43 cm 3 g −1 , respectively, using grand canonical Monte Carlo. Owing to its porosity and high electrical conductivity, GTUB3 may be used as a low-cost electrode material in next generation of supercapacitors, while its low bandgap and high photoluminescence make it a promising material for optoelectronic applications.

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“…[{Cu(terpy)] 4 Cu(VO 2 ) 4 (MTPPA‐H) 2 ] is based on the linker methane tetra‐ p ‐phenylphosphonic acid and was obtained by reaction of the linker with a mixture of CuSO 4 · 5H 2 O, Na 3 VO 4 , 2,2':6':2''‐terpyridine, HF and water at 180 °C (Figure ). The obtained three‐dimensional framework consists of a one‐dimensional chain containing octahedral coordinated Cu(II) atoms, square‐pyramidal coordinated Cu(II) atoms and tetrahedral coordinated V(V) atoms.…”

Section: Tetrahedral X‐shaped Organophosphonic Acid Linkers With Methmentioning

confidence: 99%

“…Linker molecule, inorganic building unit and MOF structure of: [{Cu(terpy)} 4 Cu(VO 2 ) 4 (MTPPA‐H) 2 ], [Co(H 4 ‐MTPPA)] 3NMP H 2 O, Zn 2 H 4 MTPPA, SZ‐2 and SZ‐3 …”

Section: Tetrahedral X‐shaped Organophosphonic Acid Linkers With Methmentioning

confidence: 99%

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

Tholen

Zorlu

Beckmann³

et al. 2020

Eur J Inorg Chem

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This review is divided into three different parts. In the introduction, the current applications of metal‐organic frameworks (MOFs) are shown. Furthermore, the overall stability, a comparison of phosphonate MOFs with carboxylate MOFs, the structural richness of phosphonate MOFs with the challenge in synthesis and different linker geometries is discussed. In the second part, several phosphonate MOFs with Y‐shaped planar, X‐shaped planar, and X‐shaped tetrahedral linker systems are described. The final part discusses different structures of inorganic building units (IBUs) with different metal atoms and a comparison of the formed MOF structures.

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A potential Cu/V-organophosphonate platform for tailored void spacesviaterpyridine mold casting

Cited by 16 publications

References 66 publications

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in O_h, T_d-cobalt(ii) tetraphenylmethane-based coordination polymers

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in O_h, T_d-cobalt(ii) tetraphenylmethane-based coordination polymers

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

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A potential Cu/V-organophosphonate platform for tailored void spacesviaterpyridine mold casting

Cited by 16 publications

References 66 publications

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in Oh, Td-cobalt(ii) tetraphenylmethane-based coordination polymers

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in Oh, Td-cobalt(ii) tetraphenylmethane-based coordination polymers

Electrically Conductive Photoluminescent Porphyrin Phosphonate Metal–Organic Frameworks

Probing Isoreticular Expansions in Phosphonate MOFs and their Applications

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Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in O_h, T_d-cobalt(ii) tetraphenylmethane-based coordination polymers

Spectrally-resolved third-harmonic generation and the fundamental role of O–H⋯Cl hydrogen bonding in O_h, T_d-cobalt(ii) tetraphenylmethane-based coordination polymers