Etude des composés d'addition des acides de LEWIS XXVII. Composés d'addition de la cyclohexanedione-1, 4 avec HgCl2, ZnCl2, et TiCl4

The adducts of cyclohexane-1,4-dione with HgCl₂, ZnCl₂, and TiCl₄ have been prepared, and the IR. absorption spectra of the solid products studied. The lowering of the carbonyl frequency shows that the acceptor is linked by dative bonds to the carbonyl oxygen donors. This result confirms the cyclohexane-1,4-dione · HgCl₂ structure which has been determined by X rays diffraction.     

Etude de composés d'addition d'acides de Lewis. XXXVI [1] Composés d'addition de l'anthraquinone-9, 10 et de l'anthrone avec divers acides de Lewis

Solid stoichiometric adducts of 9, 10-anthraquinone with SbCl₅, ZrCl₄, TiCl₄ SnCl₄, AlCl₃, have been prepared. The very important lowering Δω of the IR. carbonyl frequency, ranging from ?175 cm^?1 for SbCl₅ to ?117 cm^?1 for SnCl₄, shows that the acceptor is linked by a dative bond to the carbonyl oxygen atom acting as a donor; an assignment of most of the fundamental IR. frequencies is proposed for anthraquinone and the mentioned adducts. Similar assignments and interpretation have been made for anthrone and its solid adduct with SbCl₅, ZrCl₄, TiCl₄, SnCl₄, AlCl₃ and ZnCl₂, where the C?O lowerings range from ?164 cm^?1 for SbCl₅ to ?97 cm^?1 for ZnCl₂.     

Etude des composés d'addition d'acides de Lewis,XXXVII [1] composés d'addition de quelques quinones avec TiCl4, et relation entre les fréquences carbonyle et diverses grandeurs physicochimiques

1:1 or 1:2 solid stoichiometric adducts of TiCl₄ with anthraquinone-1,4, anthraquinone-1,2, naphtacenequinone-5,12, pentacenequinone-6,13 have been prepared. The very important lowering Δω(C?O) of the respective IR. carbonyl frequencies, ranging from ?160 to ?100 cm^?1, shows that the acceptor is linked by a dative bond to the carbonyl oxygen atom acting as donor. On the basis of calculations and various considerations, the reduction of the C?O double bond character is confirmed. Linear relations are found to exist between the oxydo-reduction or the polarographic reduction potential of the quinones, and their antisymetric ω_a(C?O) frequencies, the values of Δω, and the O → Ti vibrations, respectively.     

Etude des composés d'addition des acides de LEWIS XXIX. Composés d'addition entre acides aromatiques et SbCl5, AlCl3, TiCl4, SnCl4 ou ZnCl2

The adducts of benzoic, p-toluic, mesitoic and cinnamic acids with SbCl₅, AlCl₃, TiCl₄, SnCl₄ and ZnCl₂ have been prepared, and the IR. absorption spectra of the compounds, in the solid state or in solution in CCl₄, studied. The lowering of the carbonyl frequency shows that the acceptor is linked by a dative bond to the carbonyl oxygen atom acting as donor. A calculation, by the Wilson GF method, of force constants and their contributions in potential energy of vibration for monomeric benzoïc acid and its adduct with TiCl₄ confirmed that the carbonyl stretching force constant, and therefore the C?O bond order, is lowered by the formation of the adducts.     

Etude de composés d'addition des acides de Lewis XXVIII. Constantes de Hammett et vibration carbonyle des composés formés par TiCl4 et SbCl5 avec des chlorures de benzoyle parasubstitués

The adducts of benzoyl chlorides p-substituted by CH₃O? , CH₃? , and H? with the electronic acceptors SbCl₅ and TiCl₄ have been prepared, and the IR. absorption spectra of the solid products studied.     

Etude des composés d'addition des acides de Lewis XXX [1]. Note préliminaire sur les composés d'addition entre aldéhydes et TiCl4

The adducts of acetic, benzoic, cinnamic, and anisic aldehydes with TiCl₄ have been prepared, and the IR. spectra of the compounds, in the solid state or in solution in CH₂Cl₂, studied. The lowering of the carbonyl frequency shows that the acceptor is linked by a dative bond to the carbonyl oxygen atom acting as donor.     

Etude des composés d'addition des acides de Lewis - XXXV. Note sur les composés d'addition entre amides et,respectivement, PdCl2 et PtCl2

The adducts of dimethylformamide, diethylformamide, dimethylacetamide and diethylacetamide with PdCl₂ and PtCl₂ have been prepared and the IR. spectra of the compounds in nujol mull or in CH₂Cl · CH₂Cl solution are studied. The lowering of the carbonyl frequency (amide I) shows that the metal is linked by a dative bond to the amide oxygen atom acting as a donor; the lowering is about 33 to 59 cm^?1. The decrease of the frequency of the carbonyl group vibration, observed in these cases as for other addition compounds of Lewis acids, is due to an intramolecular electronic displacement in the direction of the amid oxygen atom.     

Syntheses,Crystal Structures,and Photocatalytic Activities of Three Copper Coordination Polymers Based on Bis(1H‐imidazol‐4‐yl)benzene/3‐(2‐Pyridyl)pyrazole

Three copper(II) coordination polymers (CuCPs), namely, [Cu_0.5(1,4‐bib)(SO₄)_0.5]_n ( 1 ), {[Cu(1,3‐bib)₂(H₂O)] · SO₄ · H₂O}_n ( 2 ), and [Cu(bpz)(SO₄)_0.5]_n ( 3 ), were assembled from the reaction of three N‐donors [1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and Hbpz = 3‐(2‐pyridyl)pyrazole] with copper sulfate under hydrothermal conditions. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric analyses (TGA). Structure analyses reveal that complex 1 is a 3D 6‐connected {4¹² · 6³}‐ pcu net, complex 2 is a fourfold 3D 4‐connected 6⁶‐ dia net, whereas complex 3 is a 1D snake‐like chain, which further expanded into 3D supramolecular architectures with the help of C–H ··· O hydrogen bonds. Moreover, the photocatalytic tests demonstrate that the obtained CuCPs are photocatalysts in the degradation of MB with the efficiency is 86.4 % for 1 , 75.3 % for 2 , and 91.3 % for 3 after 2 h, respectively.     

Metal Ion‐tuned Complexes based on Benzene‐1, 2, 4, 5‐tetracarboxylic Acid and the Semirigid Ligand 1, 4‐Bis(2‐methylbenzimidazol‐1‐ylmethyl) Benzene

Abstract. Two metal‐organic coordination polymers [Co(bmb)(btc)_0.5]_n( 1 ) and {[Zn(bmb)_0.5(btc)_0.5(H₂O)] · 0.5bmb · H₂O}_n ( 2 ) [H₄btc = benzene‐1, 2, 4, 5‐tetracarboxylic acid, bmb = 1, 4‐bis(2‐methylbenzimidazol‐1‐ylmethyl) benzene] were prepared under hydrothermal conditions. Single‐crystal X‐ray diffraction indicates that both complexes have a 2D framework structure with (4 · 6²) (4² · 6² · 8²) topology. Interestingly, the hydrogen bonds in 2 form a fascinating meso‐helix. The catalytic activity of 1 for oxidative coupling of 2, 6‐dimethylphenol (DMP) and the photoluminescence properties of 2 were investigated. Furthermore, the complexes were investigated by IR spectroscopy and thermogravimetric analysis.     

Composés d'addition des chlorures de terres rares avec le méthanol,l'éthanol et le propanol-2. Préparations,solubilités et réactions de transsolvatation

By reaction of hydrated rare earths chlorides (M = La, Nd, Sm, Gd, Dy, Er, Yb, Y) with orthoformates, the following adducts have been prepared: MCl₃· 4MeOH, MCl₃ ·3EtOH (M = La, Nd, Sm, Gd, Yb), MCl₄ · 4 EtOH (M = Dy, Er, Y); adducts MCl₃ · 3iso-PrOH have been prepared by successive action of methyl orthoformate and of 2-propanol. The solubilities of these adducts in the corresponding alcohols at 25° (for the lanthanum adducts equally at 0 and 50°) are given. Two examples of the transsolvatation of these compounds, yielding adducts with weakligands, are described.     

Composés d'addition des halogénures de niobium(V) et de tantale(V). V. Stabilité relative des composés des chlorures avec quelques oxydes et sulfures organiques

The adducts of niobium(V) and tantalum(V) chlorides with some aliphatic and cyclic oxides and sulfides, studied by NMR. spectroscopy in CHCl₃, are found to have 1:1 stoechiometry, at room temperature and lower. In the thioxane complex TaCl₅ · C₄H₈OS two species are present with the ligand coordinated by the sulfur atom or by the oxygen atom, respectively, in a proportion which has been determined. The thioxane adduct of niobium(V) chloride, however, is preferentially coordinated by the sulfur atom. There is also evidence for the species 2MCl₅ · C₄H₈OS. The relative basicity of each donor atom in dioxane, thioxane and dithiane is calculated and discussed. In contrast to the nitrile adducts, whose stability was found earlier to be controlled by inductive factors, the steric factors are more important for the ether and sulfide adducts: MCl₅ · Me₂X is more stable than the corresponding MCl₅ · Et₂X (M = Nb, Ta; X = O, S). Both niobium(V) and tantalum(V) chlorides have a soft behaviour, but NbCl₅ is a weaker Lewis acid than TaCl₅ and shows also a softer behaviour.     

A Co‐MOF with a (4,4)‐connected binodal two‐dimensional topology: synthesis,structure and photocatalytic properties

The Co‐MOF poly[[diaqua{μ₄‐1,1,2,2‐tetrakis[4‐(1H‐1,2,4‐triazol‐1‐yl)phenyl]ethylene‐κ⁴N:N′:N′′:N′′′}cobalt(II)] benzene‐1,4‐dicarboxylic acid benzene‐1,4‐dicarboxylate], {[Co(C₃₄H₂₄N₁₂)(H₂O)₂](C₈H₄O₄)·C₈H₆O₄}_n or {[Co(ttpe)(H₂O)₂](bdc)·(1,4‐H₂bdc)}_n, (I), was synthesized by the hydrothermal method using 1,1,2,2‐tetrakis[4‐(1H‐1,2,4‐triazol‐1‐yl)phenyl]ethylene (ttpe), benzene‐1,4‐dicarboxylic acid (1,4‐H₂bdc) and Co(NO₃)₂·6H₂O, and characterized by single‐crystal X‐ray diffraction, IR spectroscopy, powder X‐ray diffraction (PXRD), luminescence, optical band gap and valence band X‐ray photoelectron spectroscopy (VB XPS). Co‐MOF (I) shows a (4,4)‐connected binodal two‐dimensional topology with a point symbol of {4⁴·6²}{4⁴·6²}. The two‐dimensional networks capture free neutral 1,4‐H₂bdc molecules and bdc^2? anions, and construct a three‐dimensional supramolecular architecture via hydrogen‐bond interactions. MOF (I) is a good photocatalyst for the degradation of methylene blue and rhodamine B under visible‐light irradiation and can be reused at least five times.     

Syntheses,Crystal Structures,and Magnetic Properties of Two Cobalt Coordination Polymers Constructed From 1,3‐Bis(2,4‐dicarboxyphenyl) Benzene and Bis(imidazole) Linkers

Abstract. The 3D cobalt(II) coordination polymers [Co_1.5(HDDB)(1,4‐bib)_1.5(H₂O)]_n ( 1 ), and {[Co₂(DDB)(1,3‐bib)₂(μ₂‐H₂O)] · H₂O}_n ( 2 ) were assembled by mixed‐ligand synthetic strategy [H₄DDB = 1,3‐bis(2,4‐dicarboxyphenyl) benzene, 1,3‐bib = 1,3‐bis(1H‐imidazol‐4‐yl)benzene, and 1,4‐bib = 1,4‐bis(1H‐imidazol‐4‐yl)benzene]. Their structures were determined by single‐crystal X‐ray diffraction analyses and further characterized by elemental analyses (EA), IR spectroscopy, powder X‐ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X‐ray diffraction analysis reveals that complex 1 is an interestingly 3D (3,3.6)‐connected (6³)₄(6⁵ · 8⁸ · 10²) net, and complex 2 is an unprecedented dinuclear [Co₂(COO)(μ₂‐H₂O)] SBUs based 3D (3,6)‐connected (3 · 6 · 7)(3² · 4³ · 5⁴ · 6³ · 7 · 8²) net. Additionally, the magnetic properties of 2 were investigated.     

Two new NiII and ZnII metal–organic frameworks of glutarate and 1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene ligands: syntheses,structures and luminescence sensing properties

Two new metal–organic frameworks (MOFs), namely, three‐dimensional poly[diaquabis{μ₂‐1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene}bis(μ₂‐glutarato)dinickel(II)] monohydrate], {[Ni₂(C₅H₆O₄)₂(C₁₆H₁₈N₄)₂(H₂O)₂]·H₂O}_n or {[Ni₂(Glu)₂(1,4‐mbix)₂(H₂O)₂]·H₂O}_n, ( I ), and two‐dimensional poly[[{μ₂‐1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene}(μ₂‐glutarato)zinc(II)] tetrahydrate], {[Zn(C₅H₆O₄)(C₁₆H₁₈N₄)]·4H₂O}_n or {[Zn(Glu)(1,4‐mbix)]·4H₂O}_n ( II ), have been synthesized hydrothermally using glutarate (Glu^2?) mixed with 1,4‐bis[(2‐methyl‐1H‐imidazol‐1‐yl)methyl]benzene (1,4‐mbix), and characterized by single‐crystal X‐ray diffraction, IR and UV–Vis spectroscopy, powder X‐ray diffraction, and thermogravimetric and photoluminescence analyses. Ni^II MOF ( I ) shows a 4‐connected 3D framework with point symbol 6⁶, but is not a typical dia network. Zn^II MOF ( II ) displays a two‐dimensional 4⁴‐ sql network with one‐dimensional water chains penetrating the grids along the c direction. The solid‐state photoluminescence analysis of ( II ) was performed at room temperature and the MOF exhibits highly selective sensing toward Fe³⁺ and Cr₂O₇^2? ions in aqueous solution.     

Construction of ZnII‐based rac‐Helical Chains Containing Semi‐rigid Dipolar Ligand 1,4‐Bis(benzimidazol‐1‐ylmethyl)benzene

A Zn^II compound based on the semi‐rigid dipolar ligand 1,4‐bis(benzimidazol‐1‐ylmethyl)benzene (L), {[Zn( L )₂Cl₂]·2DMF}_n ( 1 ) has been synthesized successfully under solvothermal conditions. X‐ray single crystal diffraction shows that the complex contains P‐helical and M‐helical chains with 2₁ screw axis but crystallizes as a racemate. Through π···π stacking interactions between two well‐overlapping benzimidazoleyl rings from two adjacent chains, the 3D racemic supramolecular network is assembled. Furthermore, the IR, TGA and luminescent properties are also investigated in this work.     

Die Kristallstrukturen von PPh4[MCl5(NCMe)] · MeCN (M = Ti,Zr), zwei Modifikationen von PPh4[TiCl5(NCMe)] und von cis‐TiCl4(NCMe)2 · MeCN

The Crystal Structures of PPh₄[MCl₅(NCMe)] · MeCN (M = Ti, Zr), two Modifications of PPh₄[TiCl₅(NCMe)] and of cis ‐TiCl₄(NCMe)₂ · MeCN The title compounds were obtained by reactions of TiCl₄ or ZrCl₄, respectively, with PPh₄Cl and acetonitrile in the presence of S₂Cl₂. PPh₄[TiCl₅(NCMe)] · MeCN is unstable and emanates the incorporated acetonitrile. PPh₄[TiCl₅(NCMe)] forms the two modifications aP114 and mP228, the latter being more stable. The crystal structures were determined by X‐ray diffraction. Triclinic PPh₄[TiCl₅(NCMe)]‐(aP114) crystallizes in a distorted variety at the tetragonal AsPh₄[RuNCl₄] type, i. e. with PPh₄⁺ ions that are piled to columns in the c direction; the [TiCl₅(NCMe)]^– ions are tilted vs. this direction and thus cause the symmetry reduction from P4/n to P1. PPh₄[TiCl₅(NCMe)] · MeCN and PPh₄[ZrCl₅(NCMe)] · MeCN also have the same packing principle as in AsPh₄[RuNCl₄] with a symmetry reduction from P4/n to P112₁/n and a doubled c axis. Instead, PPh₄[TiCl₅(NCMe)]‐(mP228) has a packing with (PPh₄⁺)₂ pairs. Orthorhombic TiCl₄(NCMe)₂ · MeCN contains molecules having two acetonitrile ligands attached to the Ti atom in a cis configuration.     

Untersuchungen an Stickstoff—Jod-Verbindungen. VII. Das IR-Spektrum des Stickstofftrijodid-1-Ammoniaks im Bereich der N–J-Grundschwingungen und Kraftkonstanten der N–J-Bindungen

Studies on nitrogen iodine compounds. VII. The IR spectrum of nitrogen triiodide-1 ammonia in the range of N—I fundamental vibrations and the valence force constants of the N—I bonds New infrared spectra in the region 33—600 cm^?1 of ¹⁴NI₃ · ¹⁴NH₃, ¹⁵NI₃ · ¹⁵NH₃ and ¹⁴NI₃ · pyridine, respectively, have been obtained. In addition, the infrared spectrum of ¹⁴NI₃ · ¹⁴ND₃, which has been prepared for the first time, was obtained. All absorption frequencies can be coordinated on the ground of the molecule model for the NI₃ scaffold with 5 atoms Z₂XY₂ of the symmetry C_2v which has been proved by X ray examination. A set of force constants has been calculated by approximation. The various nitrogeniodine valence force constants are discussed.     

Comparison of conventional and synchrotron X‐ray structure deter­minations of the adduct 1,2,4,5‐tetrahydroxybenzene–2,5‐dihydroxy‐1,4‐benzoquinone (1/1) and a conventional X‐ray structure determination of 1,2,4,5‐tetrahydroxybenzene monohydrate

The X‐ray structure of 1,2,4,5‐tetra­hydroxy­benzene (benzene‐1,2,4,5‐tetrol) monohydrate, C₆H₆O₄·H₂O, (I), reveals columns of 1,2,4,5‐tetra­hydroxy­benzene parallel to the b axis that are separated by 3.364 (12) and 3.453 (11) Å. Molecules in adjacent columns are tilted relative to each other by 27.78 (8)°. Water mol­ecules fill the channels between the columns and are involved in hydrogen‐bonding interactions with the 1,2,4,5‐tetra­hydroxy­benzene mol­ecules. The crystal structure of the adduct 1,2,4,5‐tetra­hydroxy­benzene–2,5‐di­hydroxy‐1,4‐benzo­quinone (1/1), C₆H₆O₄·C₆H₄O₄, (II), reveals alternating mol­ecules of 1,2,4,5‐tetra­hydroxy­benzene and 2,5‐di­hydroxy‐1,4‐benzo­quinone (both lying on inversion centers), and a zigzag hydrogen‐bonded network connecting mol­ecules in three dimensions. For compound (II), the conventional X‐ray determination, (IIa), is in very good agreement with the synchrotron X‐ray determination, (IIb). When differences in data collection temperatures are taken into account, even the displacement parameters are in very good agreement.     

Composés d'addition des halogénures de niobium(V) et de tantale(V). VII. Composés du chlorure de niobium(V) avec l'oxytrichlorure et l'oxytribromure de phosphore

The adducts NbCl₅ · OPCl₃ and NbCl₅ · OPBr₃ are observed in chloroform solution by ³¹P-NMR spectroscopy. The enthalpy and entropy of activation for the exchange reaction between bulk and coordinated OPCl₃ are found equal to 17 ± 3 kcal/mole and 18 ± 10 cal/°mole. The stability of NbCl₅ · OPCl₃ is compared on a semi-quantitative basis to the stability of other adducts NbCl₅ · OPR₃ (R = Br, OMe, NMe₂).     

A novel three‐dimensional tetranuclear CoII coordination polymer with water hexamers based on the V‐shaped tetracarboxylate ligand 4‐(2,4‐dicarboxylatophenoxy)phthalate

A new coordination polymer (CP), namely, poly[[diaquatris[μ₂‐1,4‐bis(1H‐imidazol‐1‐yl)benzene]bis[μ₆‐4‐(2,4‐dicarboxylatophenoxy)phthalato]tetracobalt(II)] hexahydrate], {[Co₄(C₁₆H₆O₉)₂(C₁₂H₁₀N₄)₃(H₂O)₂]·6H₂O}_n, has been synthesized by solvothermal reaction. The CP was fully characterized by IR spectroscopy, elemental analysis, thermogravimetric analysis, and powder and single‐crystal X‐ray diffraction. It presents a three‐dimensional (3D) structure based on tetranuclear Co^II secondary building units (SBUs) with a tfz‐d net and point symbol (4³)₂(4⁶·6¹⁸·8⁴). The 4‐(2,4‐dicarboxyphenoxy)phthalic acid (H₄dcppa) ligands are completely deprotonated and link {Co₄(COO)₄}^4? SBUs into two‐dimensional (2D) layers. Furthermore, adjacent layers are connected by 1,4‐bis(1H‐imidazol‐1‐yl)benzene (bib) ligands, giving rise to a 3D supramolecular architecture. Interestingly, there are numerous elliptical cavities in the CP where isolated unique discrete hexameric water clusters have been observed. The results of thermogravimetric and magnetic analyses are described in detail.