Crystal Structures and Spectroscopic Properties of Metal–Organic Frameworks Based on Rigid Ligands with Flexible Functional Groups

Two rigid linear ligands with alkoxy functional groups (L1 = 4,4′-(2,5-dimethoxy-1,4-phenylene) dipyridine; L2 = 4,4′-(2,5-diethoxy-1,4-phenylene) dipyridine) incorporating carboxyl-containing auxiliary ligands (isophthalic acid = H₂IPA; terephthalic acid = H₂TPA; biphenyl-4,4′-dicarboxylate = H₂BPDC) have been adopted to build a series of complexes with M­(II) (M = Zn, Co, Cd) under solvothermal conditions. The formula of these complexes are {[Zn­(L1)­(IPA)]}_<i>n</i> (<b>1</b>), {[Zn­(L1)­(TPA)]·DMF}_<i>n</i> (<b>2</b>), {[Co­(L1)­(TPA)­(H₂O)₂]·2DMF}_<i>n</i> (<b>3</b>), {[Cd­(L1)­(TPA)­(H₂O)₂]·2DMF}_<i>n</i> (<b>4</b>), and {[Co­(L2)­(BPDC)]·0.5H₂O}_<i>n</i> (<b>5</b>). Five complexes have been characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and thermogravimetry measurements. Topological analyses reveal that complex <b>2</b> is a 6-connected <b>pcu</b> net with point symbol {4¹²·6³}, while complex <b>5</b> is a 6-connected <b>rob</b> net with point symbol {4⁸·6⁸·8}, the other complexes <b>1</b>, <b>3</b>, and <b>4</b> can be simplified as 4-connected <b>sql</b> nets with point symbol {4⁴.6²}. Complexes <b>1</b>, <b>3</b>, and <b>4</b> are 2D layer motifs, <b>2</b> and <b>5</b> are both 2-fold interpenetrating 3D frameworks. The optical absorption spectra of <b>3</b> and <b>5</b> indicate the nature of semiconductivity. The strong fluorescence emissions and long emission lifetimes of <b>1</b>, <b>2</b>, and <b>4</b> display that they are promising phosphorescent materials

Crystal Structures and Spectroscopic Properties of Metal–Organic Frameworks Based on Rigid Ligands with Flexible Functional Groups

Two rigid linear ligands with alkoxy functional groups (L1 = 4,4′-(2,5-dimethoxy-1,4-phenylene) dipyridine; L2 = 4,4′-(2,5-diethoxy-1,4-phenylene) dipyridine) incorporating carboxyl-containing auxiliary ligands (isophthalic acid = H₂IPA; terephthalic acid = H₂TPA; biphenyl-4,4′-dicarboxylate = H₂BPDC) have been adopted to build a series of complexes with M­(II) (M = Zn, Co, Cd) under solvothermal conditions. The formula of these complexes are {[Zn­(L1)­(IPA)]}_<i>n</i> (<b>1</b>), {[Zn­(L1)­(TPA)]·DMF}_<i>n</i> (<b>2</b>), {[Co­(L1)­(TPA)­(H₂O)₂]·2DMF}_<i>n</i> (<b>3</b>), {[Cd­(L1)­(TPA)­(H₂O)₂]·2DMF}_<i>n</i> (<b>4</b>), and {[Co­(L2)­(BPDC)]·0.5H₂O}_<i>n</i> (<b>5</b>). Five complexes have been characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and thermogravimetry measurements. Topological analyses reveal that complex <b>2</b> is a 6-connected <b>pcu</b> net with point symbol {4¹²·6³}, while complex <b>5</b> is a 6-connected <b>rob</b> net with point symbol {4⁸·6⁸·8}, the other complexes <b>1</b>, <b>3</b>, and <b>4</b> can be simplified as 4-connected <b>sql</b> nets with point symbol {4⁴.6²}. Complexes <b>1</b>, <b>3</b>, and <b>4</b> are 2D layer motifs, <b>2</b> and <b>5</b> are both 2-fold interpenetrating 3D frameworks. The optical absorption spectra of <b>3</b> and <b>5</b> indicate the nature of semiconductivity. The strong fluorescence emissions and long emission lifetimes of <b>1</b>, <b>2</b>, and <b>4</b> display that they are promising phosphorescent materials

Three 2D/2D → 2D or 3D Coordination Polymers: Parallel Stacked, Interpenetration, and Polycatenated

Three fascinating coordination polymers, {[Zn₂(TPPBDA)­(HCO₂^–)₄]·2H₂O}_<i>n</i> (<b>1</b>), {[Zn­(TPPBDA)_1/2(4,4′-sdb)]·2H₂O }_<i>n</i> (<b>2</b>), and {[Zn­(TPPBDA)_1/2(oba)·2DMF·2H₂O]}_<i>n</i> (<b>3</b>), have been successfully synthesized and characterized by the self-assembly of the TPPDBA ligand as well as Zn²⁺ metal salts, or in the presence of carboxylate ligands (TPPDBA = <i>N</i>,<i>N</i>,<i>N</i>′,<i>N</i>′-tetrakis­(4-(4-pyridine)-phenyl) biphenyl-4,4′-diamine), 4,4′-H₂sdb = 4,4′-sulfonyldibenzoate, 4,4′-H₂oba = 4,4′-oxybis­(benzoate), DMF = <i>N</i>,<i>N</i>-dimethylformamide). In complex <b>1</b>, the 2D ABAB parallel stacked network in which left- and right-handed helical chains coexist and array alternately (2D_chiral/2D_chiral → 2D_achiral) makes <b>1</b> give rise to a new interesting 2D interwoven network. Complex <b>2</b> exhibits a 2D + 2D → 2D parallel interpenetrated network. For compound <b>3</b>, the polycatenation among the 2D layer further extends the 2D net into a 3D framework

Construction of Metal–Organic Frameworks Based on Two Neutral Tetradentate Ligands

The solvothermal reaction of two new neutral tetradentate ligands with different bivalent metal salts gave seven metal–organic frameworks (MOFs): [Co₂(L1) (<i>trans</i>-chdc)₂]·5H₂O (<b>1</b>), [Zn₂(L1)­(<i>trans</i>-chdc)­(NO₂)₂]·DMF (<b>2</b>), [Cd₂(L1)­(<i>trans</i>-chdc)₂]·4H₂O (<b>3</b>), [Zn₂(L1)­(1,4-bdc)₂]·(H₂O)₃ (<b>4</b>), [Cd₂(L1)­(1,4-bdc)₂]·DMF·(solvent)_<i>x</i> (<b>5</b>), [Co­(L2) (<i>trans</i>-chdc)­(H₂O)]·1.5H₂O (<b>6</b>), [Co­(L2) (1,4-bdc) (H₂O)] · 2H₂O (<b>7</b>), (L1 = 1,1′-oxybis­[3,5-diimidazole]-benzene, L2 = 1,1′-oxybis­[3,5-dipyridine]-benzene, <i>trans</i>-chdc = <i>trans</i>-1,4-cyclohexanedicarboxylic acid, 1,4-bdc = 1,4-benzenedicarboxylate). These MOFs were prepared to examine the effects of the core metal ion or organic ligand on the topology and interpenetration form. The results show that the imidazole ligand can rotate easily to coordinate to metal ions, while pyridine ligand exhibits the weaker coordinative abilities, which may influence the self-assembly. Compounds <b>1</b>, <b>3</b>, and <b>5</b> are three-dimensional (3D) frameworks with 2-fold interpenetrated forms, whereas complex <b>4</b> shows a 3-fold interpenetrated structure. Interestingly, compound <b>2</b> exhibits a 4-fold interpenetration. Compound <b>6</b> features a two-dimensional polymeric layer structure which exhibits a rare 2-fold interpenetrating 3D <b>hms</b> array if H-bonds are taken into account. For compound <b>7</b>, the dinuclear cobalt secondary building unit (SBU) assembles with mixed ligands L2 and 1,4-bdc to construct a 3D α-<b>Po</b> structure

Construction of Metal–Organic Frameworks Based on Two Neutral Tetradentate Ligands

The solvothermal reaction of two new neutral tetradentate ligands with different bivalent metal salts gave seven metal–organic frameworks (MOFs): [Co₂(L1) (<i>trans</i>-chdc)₂]·5H₂O (<b>1</b>), [Zn₂(L1)­(<i>trans</i>-chdc)­(NO₂)₂]·DMF (<b>2</b>), [Cd₂(L1)­(<i>trans</i>-chdc)₂]·4H₂O (<b>3</b>), [Zn₂(L1)­(1,4-bdc)₂]·(H₂O)₃ (<b>4</b>), [Cd₂(L1)­(1,4-bdc)₂]·DMF·(solvent)_<i>x</i> (<b>5</b>), [Co­(L2) (<i>trans</i>-chdc)­(H₂O)]·1.5H₂O (<b>6</b>), [Co­(L2) (1,4-bdc) (H₂O)] · 2H₂O (<b>7</b>), (L1 = 1,1′-oxybis­[3,5-diimidazole]-benzene, L2 = 1,1′-oxybis­[3,5-dipyridine]-benzene, <i>trans</i>-chdc = <i>trans</i>-1,4-cyclohexanedicarboxylic acid, 1,4-bdc = 1,4-benzenedicarboxylate). These MOFs were prepared to examine the effects of the core metal ion or organic ligand on the topology and interpenetration form. The results show that the imidazole ligand can rotate easily to coordinate to metal ions, while pyridine ligand exhibits the weaker coordinative abilities, which may influence the self-assembly. Compounds <b>1</b>, <b>3</b>, and <b>5</b> are three-dimensional (3D) frameworks with 2-fold interpenetrated forms, whereas complex <b>4</b> shows a 3-fold interpenetrated structure. Interestingly, compound <b>2</b> exhibits a 4-fold interpenetration. Compound <b>6</b> features a two-dimensional polymeric layer structure which exhibits a rare 2-fold interpenetrating 3D <b>hms</b> array if H-bonds are taken into account. For compound <b>7</b>, the dinuclear cobalt secondary building unit (SBU) assembles with mixed ligands L2 and 1,4-bdc to construct a 3D α-<b>Po</b> structure

An Unprecedented Homochiral Metal–Organic Framework Based on Achiral Nanosized Pyridine and V‑Shaped Polycarboxylate Acid Ligand

A unique homochiral metal–organic framework has been successfully synthesized by solvothermal reaction of an achiral flexible V-shaped ligand and a nanosized π-electron-deficient pyridine ligand based on cobalt­(II) salt, [Co­(L)­(DPNDI)_0.5]_<i>n</i> (<b>1</b>) (H₂L = 4,4′-dicarboxydiphenylamine, DPNDI = <i>N</i>,<i>N</i>′-di-(4-pyridyl)-1,4,5,8-naphthalenediimide); the helixes assembled by H₂L and cobalt­(II) paddle-wheel centers are left-handed and transform the framework to chiral. Also, the inserting of the DPNDI transforms the original <b>dia</b> net constructed by H₂L and cobalt­(II) paddle-wheel centers to a 3-fold <b>jsm</b> net. This is the first example of interpenetrated <b>jsm</b> net. In addition, the chiral property of bulk products is confirmed by circular dichroism spectra (CD), and the thermal stability and the magnetic properties are also investigated

DataSheet1_Research on the facile regeneration of degraded cathode materials from spent LiNi0.5Co0.2Mn0.3O2 lithium-ion batteries.docx

Rational reusing the waste materials in spent batteries play a key role in the sustainable development for the future lithium-ion batteries. In this work, we propose an effective and facile solid-state-calcination strategy for the recycling and regeneration of the cathode materials in spent LiNi0.5Co0.2Mn0.3O2 (NCM523) ternary lithium-ion batteries. By systemic physicochemical characterizations, the stoichiometry, phase purity and elemental composition of the regenerated material were deeply investigated. The electrochemical tests confirm that the material characteristics and performances got recovered after the regeneration process. The optimal material was proved to exhibit the excellent capacity with a discharge capacity of 147.9 mAh g−1 at 1 C and an outstanding capacity retention of 86% after 500 cycles at 1 C, which were comparable to those of commercial NCM materials.</p

Distribution of EDE-Q scores in the AN patients with the three 5-HTTLPR genotypes.

<p>The <i>P</i>-values were adjusted for sex, age, BMI, education and age at onset.</p><p>EDE-Q, Eating Disorder Examination Questionnaire.</p><p>Distribution of EDE-Q scores in the AN patients with the three 5-HTTLPR genotypes.</p

Demographic features in AN patients and controls.

<p>BMI, body mass index; EDE-Q, Eating Disorder Examination Questionnaire.</p><p>Demographic features in AN patients and controls.</p

Tuning Structural Topologies of a Series of Metal–Organic Frameworks: Different Bent Dicarboxylates

Five new metal–organic frameworks incorporating the angular tetratopic ligand with different transition metal ions and bent coligands have been synthesized: [Zn₄(L)₂(4,4′-sdb)₄(H₂O)₂]·3H₂O (<b>1</b>), [Zn₂(L)₂(hfipbb)₂(H₂O)₃] (<b>2</b>), [Zn­(L)­(oba)]·H₂O (<b>3</b>), [Cd₂(L)₂(4,4′-sdb)₂]·2H₂O (<b>4</b>), [Cd₂(L)­(hfipbb)­(H₂O)₃]·2H₂O (<b>5</b>), [L = 1,1′-oxybis­[3,5-dipyridine-benzene, 4,4′-H₂sdb = 4,4′-sulfonyldibenzoate, H₂hfipbb = 4,4′-(hexafluoroisopropylidene)­bis­(benzoic acid), H₂oba = 4,4′-oxybis­(benzoate)]. Structural analysis reveals that the mixed ligands display versatile coordination modes to manage the metal ions to form homochiral, inclined polycatenation (1D → 2D), 3-fold interpenetrating nets. However, the different coordinated modes, geometry, and flexibility of ligands around metal ions result in subtle differences in the final architecture. Bulk materials for <b>1</b> and <b>3</b> have a second-harmonic generation activity, approximately 0.4 and 0.8 times that of urea