Template-Directed Selective Photodimerization Reactions of 5-Arylpenta-2,4-dienoic Acids.

We developed an efficient method that enables selective photodimerization of 5-arylpenta-2,4-dienoic acids (i.e., vinylogous cinnamic acids). The use of 1,8-dihydroxynaphthalene as a template ensures proximity of the two reacting olefins so that irradiation of template-bound dienoic acids gives mono [2 + 2] cycloaddition products in good to excellent yields (up to 99%), as single regioisomers, and with high diastereoselectivities (dr = 3:1 to 13:1). The geometrical and stereochemical features of compounds 12a, 16a, and 22a were analyzed by X-ray crystallography.

New solvated Mo(VI) complexes of isatin based asymmetric bisthiocarbohydrazones as potent bioactive agent: synthesis, DFT-molecular docking studies, biological activity evaluation and crystal structures.

New solvated Mo(VI) complexes were isolated from the reaction of [MoO2(acac)2] with asymmetric isatin bisthiocarbohydrazone ligands. The ligands were obtained from the reaction of isatin monothiocarbohydrazone with 3,5-dibromo salicylaldehyde (L1), 3,5-dichloro salicylaldehyde (L2) and 3-chloro-5-bromo salicylaldehyde (L3), respectively. In the complexes, the ligands serve as ONS donors and coordinate to the [MoO2]2+ nucleus. The bonding sites are azomethine nitrogen atom, phenolic oxygen atom and thiol sulfur atom. The sixth coordination site is completed by an oxygen atom from an ethanol solvent. The ethanol-coordinated Mo(VI) complexes, C1-C3, [MoO2L(EtOH)] (L: L1-L3), were characterized using elemental analysis, IR and 1H NMR spectroscopies, and conductivity measurements. By crystallizing ethanol-solvated solid complexes from an EtOH/DMSO mixture, DMSO-solvated complexes (C4-C6) suitable for X-ray crystallography were obtained. Crystal structure analysis supports the proposed complex structures and geometries, but the ethanol in the sixth coordination site has been replaced by DMSO. When the anticarcinogenic effects of the ligands and complexes (C1-C3) on the C6 cell line were examined, it was found that the complexes showed higher activity than the ligands. The C3 complex appears to have the best anti-cancer activity compared to doxorubicin. Additionally, all compounds were determined to have high total antioxidant capacity. Data obtained from theoretical studies (DFT and docking) support experimental studies.

A New Family of Layered Metal-Organic Semiconductors: Cu/V-Organophosphonates.

Herein, we report the design and synthesis of a layered redox-active, antiferromagnetic metal organic semiconductor crystals with the chemical formula [Cu(H2 O)2 V(µ-O)(PPA)2 ] (where PPA is phenylphosphonate). The crystal structure of [Cu(H2 O)2 V(µ-O)(PPA)2 ] shows that the metal phosphonate layers are separated by phenyl groups of the phenyl phosphonate linker. Tauc plotting of diffuse reflectance spectra indicates that [Cu(H2 O)2 V(µ-O)(PPA)2 ] has an indirect band gap of 2.19 eV. Photoluminescence (PL) spectra indicate a complex landscape of energy states with PL peaks at 1.8 and 2.2 eV. [Cu(H2 O)2 V(µ-O)(PPA)2 ] has estimated hybrid ionic and electronic conductivity values between 0.13 and 0.6 S m-1 . Temperature-dependent magnetization measurements show that [Cu(H2 O)2 V(µ-O)(PPA)2 ] exhibits short range antiferromagnetic order between Cu(II) and V(IV) ions. [Cu(H2 O)2 V(µ-O)(PPA)2 ] is also photoluminescent with photoluminescence quantum yield of 0.02%. [Cu(H2 O)2 V(µ-O)(PPA)2 ] shows high electrochemical, and thermal stability.

Engineering supramolecular helical assemblies via interplay between carbon(sp) tetrel and halogen bonding interactions.

Building supramolecular helical structures is a challenge due to difficulties in the design and control of competitive noncovalent forces. Herein, we report three scaffolds (1a, 1b, and 1c) decorated with -CN and -Br groups. These groups known for their ability to form multiple noncovalent interactions and with efficient design can be utilized to achieve such complex structures. X-Ray analyses revealed that the crystal packing of 1a, 1b and 1c is dominated by highly directional Br⋯CN Csp-tetrel bonding (1a), Br⋯π, Br⋯N (1b) and Br⋯Br (1c) XB interactions, and these interactions have led to the formation of achiral P/M, chiral M and achiral P/M helical assemblies, respectively. A detailed structural and computational analysis was performed to clarify the nature and estimate the strength of these interactions in helical assemblies. MEP analyses of 1a, 1b, and 1c have shown that the potential of electron-deficient and electron-rich regions within the structures has similar values. Yet, the geometric accessibility of σ-holes has differed with each scaffold. Thus, dominant interactions have changed and consequently led to different helical assembly formations. The interaction energies are around -11.4 (1a), -4.0 (1b), and -4.6 (1c) kcal mol-1 and mainly driven by dispersion, followed by electrostatic interactions. To our surprise, the Csp-tetrel bonding (1a), considered the weakest among non-covalent interactions, is the strongest interaction among the three scaffolds, which shows the importance of accessibility of Sigma holes. These findings are expected to contribute to the future rational design of complex self-assembled materials, utilizing Csp-tetrel and XB interactions, in various applications such as crystal engineering, organic semiconductors, sensor devices, and medicinal chemistry.

Bromination of endo-7-norbornene derivatives revisited: failure of a computational NMR method in elucidating the configuration of an organic structure.

Previously we reported on the bromination of endo-7-bromonorbornene at different temperatures yielding mixtures of addition products. The structural elucidations of the formed compounds were achieved by NMR spectroscopy. Particularly, the γ-gauche effect and long-range couplings were instrumental in assigning the stereochemistry of the adducts. However, in a recent paper, Novitskiy and Kutateladze claimed that based on an applied machine learning-augmented DFT method for computational NMR that the structure of the product, (1R,2R,3S,4S,7s)-2,3,7-tribromobicyclo[2.2.1]heptane was wrong. With the aid of their computational method, they revised a number of published structures, including ours, and assigned our product the structure (1R,2S,3R,4S,7r)-2,3,7-tribromobicyclo[2.2.1]heptane. To fit their revised structure, they proposed an alternative mechanism featuring a skeletal rearrangement without the intermediacy of a carbocation. Herein, we are not only confirming the structure originally assigned by us through crucial NMR experiments, we also present the ultimate structural proof by means of X-ray crystallography. Moreover, we disprove the mechanism proposed by the aforementioned authors based on sound mechanistic reasoning and point to an oversight by the authors that led them to an erroneous mechanistic pathway.

Tuning Structural and Optical Properties of Porphyrin-based Hydrogen-Bonded Organic Frameworks by Metal Insertion.

Herein, 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.

New Pd(II) complexes of the bisthiocarbohydrazones derived from isatin and disubstituted salicylaldehydes: Synthesis, characterization, crystal structures and inhibitory properties against some metabolic enzymes.

Pd(II) complexes (Pd1, Pd2, and Pd3) were synthesized for the first time using asymmetric isatin bisthiocarbohydrazone ligands and PdCl2(PPh3)2. All complexes were characterized by a range of spectroscopic and analytical techniques. The molecular structures of Pd1 and Pd3 have been determined by single-crystal X-ray diffraction analysis. The complexes are diamagnetic and exhibit square planar geometry. The asymmetric isatin bisthiocarbohydrazone ligands coordinate to Pd(II) ion in a tridentate manner, through the phenolic oxygen, imine nitrogen and thiol sulfur, forming five- and six-membered chelate rings within their structures. The fourth coordination site in these complexes is occupied by PPh3 (triphenylphosphine). The free ligands and their Pd(II) complexes were evaluated for their carbonic anhydrase I, II (hCAs) and acetylcholinesterase (AChE) inhibitor activities. They showed a highly potent inhibition effect on AChE and hCAs. Ki values are in the range of 9 ± 0.6 - 30 ± 5.4 nM for AChE, 7 ± 0.5 - 16 ± 2.2 nM for hCA I and 3 ± 0.3-24 ± 1.9 nM for hCA II isoenzyme. The results clearly demonstrated that the ligands and their Pd(II) complexes effectively inhibited the used enzymes.

Coordination-Induced Band Gap Reduction in a Metal-Organic Framework.

Herein, we report on the synthesis of a microporous, three-dimensional phosphonate metal-organic framework (MOF) with the composition Cu3 (H5 -MTPPA)2 ⋅ 2 NMP (H8 -MTPPA=methane tetra-p-phenylphosphonic acid and NMP=N-methyl-2-pyrrolidone). This MOF, termed TUB1, has a unique one-dimensional inorganic building unit composed of square planar and distorted trigonal bipyramidal copper atoms. It possesses a (calculated) BET surface area of 766.2 m2 /g after removal of the solvents from the voids. The Tauc plot for TUB1 yields indirect and direct band gaps of 2.4 eV and 2.7 eV, respectively. DFT calculations reveal the existence of two spin-dependent gaps of 2.60 eV and 0.48 eV for the alpha and beta spins, respectively, with the lowest unoccupied crystal orbital for both gaps predominantly residing on the square planar copper atoms. The projected density of states suggests that the presence of the square planar copper atoms reduces the overall band gap of TUB1, as the beta-gap for the trigonal bipyramidal copper atoms is 3.72 eV.

A neural network potential for the IRMOF series and its application for thermal and mechanical behaviors.

Metal-organic frameworks (MOFs) with their exceptional porous and organized structures have been the subject of numerous applications. Predicting the bulk properties from atomistic simulations requires the most accurate force fields, which is still a major problem due to MOFs' hybrid structures governed by covalent, ionic and dispersion forces. Application of ab initio molecular dynamics to such large periodic systems is thus beyond the current computational power. Therefore, alternative strategies must be developed to reduce computational cost without losing reliability. In this work, we construct a generic neural network potential (NNP) for the isoreticular metal-organic framework (IRMOF) series trained by PBE-D4/def2-TZVP reference data of MOF fragments. We confirmed the success of the resulting NNP on both fragments and bulk MOF structures by prediction of properties such as equilibrium lattice constants, phonon density of states and linker orientation. The RMSE values of energy and force for the fragments are only 0.0017 eV atom-1 and 0.15 eV Å-1, respectively. The NNP predicted equilibrium lattice constants of bulk structures, even though not included in training, are off by only 0.2-2.4% from experimental results. Moreover, our fragment based NNP successfully predicts the phenylene ring torsional energy barrier, equilibrium bond distances and vibrational density of states of bulk MOFs. Furthermore, the NNP enables revealing the odd behaviors of selected MOFs such as the dual thermal expansion properties and the effect of mechanical strain on the adsorption of hydrogen and methane molecules. The NNP based molecular dynamics (MD) simulations suggest IRMOF-4 and IRMOF-7 to have positive-to-negative thermal expansion coefficients while the rest to have only negative thermal expansion at the studied temperatures of 200 K to 400 K. The deformation of the bulk structure by reduction of the unit cell volume has been shown to increase the volumetric methane uptake in IRMOF-1 but decrease the volumetric methane uptake in IRMOF-7 due to the steric hindrance. To the best of our knowledge, this study presents the first pre-trained model publicly available giving the opportunity for the researchers in the field to investigate different aspects of IRMOFs by performing large-scale simulation at the first-principles level of accuracy.

Dimethoxyindoles based thiosemicarbazones as multi-target agents; synthesis, crystal interactions, biological activity and molecular modeling.

Alzheimer's disease (AD) is known as one of the most devastating neurodegenerative disease diagnosed for the old-aged people and cholinesterase inhibitors (ChEI) can be used as an effective palliative treatment for AD. A range of novel monomeric and dimeric indole based thiosemicarbazone derivatives 17-28 was synthesized in order to target cholinesterases (ChE). Biological importance of the targeted compounds 17-28 was investigated by employing the acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) enzymes along with three different antioxidant property determination assays, namely DPPH free radical scavenging, ABTS cationic radical decolarization, and CUPRAC cupric reducing antioxidant capacity. The compounds 18 and 19 displayed the best inhibitor activity against BChE with IC50 values of 7.42 and 1.95 µM, respectively. The antioxidant potentials were found to be moderate for DPPH and ABTS assays and the compounds 28 and 18 were the most potent candidates for both antioxidant assays. Cupric reducing capacity was the most promising assay and the compounds 25, 26 and 28 provided better inhibition values than all the standards. Further binding mode and affinity studies performed by molecular docking and molecular dynamics simulations. Accordingly, the compound 19 is the most plausible candidate that can compete with galantamine (GNT), a common pharmaceutics targeting both cholinesterase enzymes.

Arylphosphonate-Tethered Porphyrins: Fluorescence Silencing Speaks a Metal Language in Living Enterocytes*.

We report the application of a highly versatile and engineerable novel sensor platform to monitor biologically significant and toxic metal ions in live human Caco-2 enterocytes. The extended conjugation between the fluorescent porphyrin core and metal ions through aromatic phenylphosphonic acid tethers generates a unique turn off and turn on fluorescence and, in addition, shifts in absorption and emission spectra for zinc, cobalt, cadmium and mercury. The reported fluorescent probes p-H8 TPPA and m-H8 TPPA can monitor a wide range of metal ion concentrations via fluorescence titration and also via fluorescence decay curves. Cu- and Zn-induced turn off fluorescence can be differentially reversed by the addition of common chelators. Both p-H8 TPPA and m-H8 TPPA readily pass the mammalian cellular membrane due to their amphipathic character as confirmed by confocal microscopic imaging of living enterocytes.

Halogen-Bonded BODIPY Frameworks with Tunable Optical Features*.

The ability to tune the optical features of BODIPY materials in the solid state is essential for their photorelated application and requires efficient control of the crystal packing. In this study, such control of BODIPY supramolecular assemblies was achieved by deliberate design and synthesis of a BODIPY containing a strong halogen-bond (XB) acceptor (-NO2 ) and donor (I, Br) to mediate XB interactions. The di-halogenated structures formed isostructural mono-coordinate motif B3, B4 (1D tubular structure) and symmetric bifurcated motif B4-II (1D zigzag chains structure) through N-O⋅⋅⋅I, Br XB interactions. These XB interactions promote singlet-to-triplet intersystem crossing and triplet-to-singlet reverse intersystem crossing due to partial delocalization of oxygen electrons onto Br and I, which leads to unexpected fluorescence enhancement of B4-II. Finally, the indirect optical band gaps of B3, B4 and B4-II were amenable to tuning in the range of 1.85-2.50 eV by XB-driven crystal packings.

Cu(II) complex with auxin (3-indoleacetic acid) and an aromatic planar ligand: synthesis, crystal structure, biomolecular interactions and radical scavenging activity.

A novel water soluble ternary copper(II) complex,-[Cu2(phen)2(3-IAA)2(H2O)](ClO4)2·H2O-(phen: 1,10-phenanthroline, 3-IAA: 3-indoleacetic acid), has been synthesized and characterized by elemental CHN analysis, ESI-TOF, FTIR and single-crystal X-ray diffraction techniques. Interaction of the complex with calf thymus DNA (CT-DNA) has been investigated by absorption spectral titration, ethidium bromide (EB) and Hoechst 33258 displacement assay. The interactions between the complex and bovine serum albumin (BSA) were investigated by electronic absorption and fluorescence spectroscopy methods. The experimental results indicate that the fluorescence quenching mechanism between the complex and BSA is a static quenching process. The Stern-Volmer constants, binding constants, binding sites and the corresponding thermodynamic parameters (ΔG, ΔH, ΔS) of BSA + complex systems were determined at different temperatures. The binding distance between the complex and BSA was calculated according to Förster non-radiation energy transfer theory (FRET). The effect of the complex on the conformation of BSA was also examined using synchronous, two dimensional (2D) and three dimensional (3D) fluorescence spectroscopy. Furthermore, the oxygen radical scavenging activity of the complex was determined in terms of IC50, using the DPPH and H2O2 method, to show that it particularly enables electron loss from radical species. This study highlights the importance of indole and moieties in the development of antioxidant agents. A potent drug candidate novel water soluble ternary copper(II) complex,-[Cu2(phen)2(3-IAA)2(H2O)] (ClO4)2·H2O-(phen: 1,10-phenanthroline, 3-IAA: 3-indoleacetic acid), has been synthesized and characterized by elemental CHN analysis, FTIR, ESI-MS and single-crystal X-ray diffraction techniques. The complex has been tested for in vitro biomacromolecular interactions by spectroscopic methods. Furthermore, radical scavenging activities of the complex were also investigated.

Template-Directed Photochemical Homodimerization and Heterodimerization Reactions of Cinnamic Acids.

We developed a general method for the selective photochemical homo- and heterodimerization of cinnamic acid derivatives with the use of commercially available 1,8-dihydroxynaphthalene as a covalent template. A variety of symmetrical and unsymmetrical ß-truxinic acids were obtained in high yields and as single diastereomers. The use of a template not only provides the alignment of the two olefins with suitable proximity (<4.2 Å) but also allows the heterodimerization of two different cinnamic acids, leading to unsymmetrical ß-truxinic acid products.

Synthesis, X-ray crystal structure, IR and Raman spectroscopic analysis, quantum chemical computational and molecular docking studies on hydrazone-pyridine compound: As an insight into the inhibitor capacity of main protease of SARS-CoV2.

The characterization and synthesis of 3-chloro-2-{(2E)-2-[1-(4-chlorophenyl)ethylidene]hydrazinyl}pyridine (CCPEHP) was investigated in our study. Mass and UV-visible spectra were recorded in chloroform solvent. The CCPEHP molecule containing pyridine and chlorophenyl rings and hydrazone group crystallized in the triclinic system and P-1 space group. FTRaman and FTIR spectra were performed in the solid state. The optimized geometry of CCPEHP was computed by DFT/B3LYP method with 6-311 G (d, p) and 6-31 G (d, p) levels. The computed vibrational analysis, electronic absorption spectrum, electronic properties, molecular electrostatic potential, natural bond orbitals analysis and other calculated structural parameters were determined by using the DFT/B3LYP/6-31 G (d, p) basis set. The correlation of fundamental modes of the compound and the complete vibrational assignments analysis were studied. The strong and weak contacts were identified by using Hirshfeld surface analysis. The molecular modeling results showed that CCPEHP structure strongly binds to COVID-19 main protease by relative binding affinity of -6.4 kcal/mol.

Fluorescent Arylphosphonic Acids: Synergic Interactions between Bone and the Fluorescent Core.

Herein, we report the third generation of fluorescent probes (arylphosphonic acids) to target calcifications, particularly hydroxyapatite (HAP). In this study, we use highly conjugated porphyrin-based arylphosphonic acids and their diesters, namely 5,10,15,20-tetrakis[m-(diethoxyphosphoryl)phenyl]porphyrin (m-H8 TPPA-OEt8 ) and 5,10,15,20-tetrakis [m-phenylphosphonic acid]porphyrin (m-H8 TPPA), in comparison with their positional isomers 5,10,15,20-tetrakis[p-(diisopropoxyphosphoryl)phenyl]porphyrin (p-H8 TPPA-iPr8 ) and 5,10,15,20-tetrakis [p-phenylphosphonic acid]porphyrin (p-H8 TPPA), which have phosphonic acid units bonded to sp2 carbon atoms of the fluorescent core. The conjugation of the fluorescent core is thus extended to the (HAP) through sp2 -bonded -PO3 H2 units, which generates increased fluorescence upon HAP binding. The resulting fluorescent probes are highly sensitive towards the HAP in rat bone sections. The designed probes are readily taken up by cells. Due to the lower reported toxicity of (p-H8 TPPA), these probes could find applications in monitoring bone resorption or adsorption, or imaging vascular or soft tissue calcifications for breast cancer diagnosis etc.

A Nanotubular Metal-Organic Framework with a Narrow Bandgap from Extended Conjugation*.

A one-dimensional nanotubular metal-organic framework (MOF) [Ni(Cu-H4 TPPA)]⋅2 (CH3 )2 NH2 + (H8 TPPA=5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin) constructed by using the arylphosphonic acid H8 TPPA is reported. The structure of this MOF, known as GTUB-4, was solved by using single-crystal X-ray diffraction and its geometric accessible surface area was calculated to be 1102 m2 g-1 , making it the phosphonate MOF with the highest reported surface area. Due to the extended conjugation of its porphyrin core, GTUB-4 possesses narrow indirect and direct bandgaps (1.9 eV and 2.16 eV, respectively) in the semiconductor regime. Thermogravimetric analysis suggests that GTUB-4 is thermally stable up to 400 °C. Owing to its high surface area, low bandgap, and high thermal stability, GTUB-4 could find applications as electrodes in supercapacitors.

In Silico Investigation into H2 Uptake in MOFs: Combined Text/Data Mining and Structural Calculations.

Metal-organic frameworks (MOFs) with high surface areas and adjustable lattice structures are attractive for gas storage and thus have been a great interest in research. Although tremendous amount of data on MOFs have been available in the literature, there are very few studies considering methodological approach for H2 uptake properties of MOFs. In this study, we systematically investigated the H2 uptake capabilities of MOFs by means of text and data mining (TDM) through retrieving data of the surface areas (SA) and pore volumes (PV) from published manuscripts. In addition, we calculated theoretical SA and PV values of all real MOFs available in Cambridge Structural Database (CSD). Prior to calculation, we applied an automated structure analysis algorithm that loads the coordinates of molecules from CSD experimental X-ray single-crystal structure and removes guest/solvent contaminants from the structure. We compared SA, PV, and H2 uptake data from both TDM and structural calculation techniques and unraveled a list of MOFs with H2 uptakes predicted from both experimental and theoretical SA/PV values that may be regarded as the most promising candidates for H2 storage. The extensive and systematic TDM strategy estimates 5975 experimental SA and 7748 experimental PV values (2080 MOFs with SA + PV values) with 78-82% success rate. In addition, structural calculations reveal the theoretical SA and PV values along with a theoretical H2 adsorption limit of MOFs in the absence of guest molecules. Combination of both TDM and structural calculation strategies provides a more comprehensive perspective for the investigation of hydrogen storage capacities in MOFs, which elucidates plausibility of new compounds as candidates for H2 storage materials.

Electrophoresis and Biosensor-Based DNA Interaction Analysis of the First Paraben Derivatives of Spermine-Bridged Cyclotriphosphazenes.

Cancer is the uncontrolled growth of abnormal cells via malignant cell division and rapid DNA replication. While DNA damaging molecules can cause cancer, their role as anticancer drugs are very significant. For this purpose, the novel series of paraben substituted spermine bridged(dispirobino) cyclotriphosphazene compounds 2-6 were synthesized for the first time, and their structures were characterized by various spectroscopic techniques. The solid-state structures and geometries of compounds 2-6 were determined using single-crystal X-ray structural analysis. In addition, it was confirmed by TGA that all compounds 1-6 showed high thermal stability. Two methods were used in order to investigate DNA interaction properties of the targeted molecules. While biosensor-based screening test that measures DNA hybridization efficiency on a biochip surface, the agarose gel electrophoresis method examines the effect of compounds on plasmid DNA structure. The results collected from the automated biosensor device and agarose gel electrophoresis have indicated that compounds 1, 5, and 6 showed higher DNA damage than the compounds 2-4. According to the biosensor results, compounds 1, 5, and 6 showed 85%, 69%, and 77% activity, respectively.

Alkali Phosphonate Metal-Organic Frameworks.

A new family of porous metal-organic frameworks (MOFs), namely alkali phosphonate MOFs, is reported. [Na2 Cu(H4 TPPA)]⋅(NH2 (CH3 )2 )2 (GTUB-1) was synthesized using the tetratopic 5,10,15,20-tetrakis[p-phenylphosphonic acid] porphyrin (H8 -TPPA) linker with planar X-shaped geometrical core. GTUB-1 is composed of rectangular void channels with BET surface area of 697 m2 g-1 . GTUB-1 exhibits exceptional thermal stability. The toxicity analysis of the (H8 -TPPA) linker indicates that it is well tolerated by an intestinal cell line, suggesting its suitability for creating phosphonate MOFs for biological applications.