scholarly journals Solvent-vapour-assisted pathways and the role of pre-organization in solid-state transformations of coordination polymers

IUCrJ ◽  
2015 ◽  
Vol 2 (2) ◽  
pp. 188-197 ◽  
Author(s):  
James S. Wright ◽  
Iñigo J. Vitórica-Yrezábal ◽  
Harry Adams ◽  
Stephen P. Thompson ◽  
Adrian H. Hill ◽  
...  

A family of one-dimensional coordination polymers, [Ag4(O2C(CF2)2CF3)4(phenazine)2(arene)n]·m(arene),1(arene = toluene or xylene), have been synthesized and crystallographically characterized. Arene guest loss invokes structural transformations to yield a pair of polymorphic coordination polymers [Ag4(O2C(CF2)2CF3)4(phenazine)2],2aand/or2b, with one- and two-dimensional architectures, respectively. The role of pre-organization of the polymer chains of1in the selectivity for formation of either polymorph is explored, and the templating effect of toluene andp-xylene overo-xylene orm-xylene in the formation of arene-containing architecture1is also demonstrated. The formation of arene-free phase2b, not accessible in a phase-pure form through other means, is shown to be the sole product of loss of toluene from1-tol·tol[Ag4(O2C(CF2)2CF3)4(phenazine)2(toluene)]·2(toluene), a phase containing toluene coordinated to Ag(I) in an unusual μ:η1,η1manner. Solvent-vapour-assisted conversion between the polymorphic coordination polymers and solvent-vapour influence on the conversion of coordination polymers1to2aand2bis also explored. The transformations have been examined and confirmed by X-ray diffraction, NMR spectroscopy and thermal analyses, includingin situdiffraction studies of some transformations.

Inorganics ◽  
2021 ◽  
Vol 9 (7) ◽  
pp. 54
Author(s):  
Giacomo Manfroni ◽  
Simona S. Capomolla ◽  
Alessandro Prescimone ◽  
Edwin C. Constable ◽  
Catherine E. Housecroft

The isomers 4′-(4-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (1), 4′-(3-(trifluoromethyl)phenyl)-4,2′:6′,4″-terpyridine (2), 4′-(4-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (3), and 4′-(3-(trifluoromethyl)phenyl)-3,2′:6′,3″-terpyridine (4) have been prepared and characterized. The single crystal structures of 1 and 2 were determined. The 1D-polymers [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 (Hhfacac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione), [Cu(hfacac)2(2)]n.2nC6H5Me, [Cu2(hfacac)4(3)2]n.nC6H4Cl2, [Cu2(hfacac)4(3)2]n.nC6H5Cl, and [Cu(hfacac)2(4)]n.nC6H5Cl have been formed by reactions of 1, 2, 3 and 4 with [Cu(hfacac)2].H2O under conditions of crystal growth by layering and four of these coordination polymers have been formed on a preparative scale. [Cu2(hfacac)4(1)2]n.2nC6H4Cl2 and [Cu(hfacac)2(2)]n.2nC6H5Me are zig-zag chains and the different substitution position of the CF3 group in 1 and 2 does not affect this motif. Packing of the polymer chains is governed mainly by C–F...F–C contacts, and there are no inter-polymer π-stacking interactions. The conformation of the 3,2′:6′,3″-tpy unit in [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl differs, leading to different structural motifs in the 1D-polymer backbones. In [Cu(hfacac)2(4)]n.nC6H5Cl, the peripheral 3-CF3C6H4 unit is accommodated in a pocket between two {Cu(hfacac)2} units and engages in four C–Hphenyl...F–Chfacac contacts which lock the phenylpyridine unit in a near planar conformation. In [Cu2(hfacac)4(3)2]n.nC6H4Cl2 and [Cu(hfacac)2(4)]n.nC6H5Cl, π-stacking interactions between 4′-trifluoromethylphenyl-3,2′:6′,3″-tpy domains are key packing interactions, and this contrasts with the packing of polymers incorporating 1 and 2. We use powder X-ray diffraction to demonstrate that the assemblies of the coordination polymers are reproducible, and that a switch from a 4,2′:6′,4″- to 3,2′:6′,3″-tpy metal-binding unit is accompanied by a change from dominant C–F...F–C and C–F...H–C contacts to π-stacking of arene domains between ligands 3 or 4.


2016 ◽  
Vol 72 (8) ◽  
pp. 1214-1218 ◽  
Author(s):  
Montserrat Alfonso ◽  
Helen Stoeckli-Evans

The isotypic title one-dimensional coordination polymers, [CdCl2(C18H14N4O4)]n, (I), and [HgCl2(C18H14N4O4)]n, (II), are, respectively, the cadmium(II) and mercury(II) complexes of the dimethyl ester of 5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylic acid. In both compounds, the metal ions are located on a twofold rotation axis and a second such axis bisects the Car—Carbonds of the pyrazine ring. The metal ions are bridged by binding to the N atoms of the two pyridine rings and have anMN2Cl2bisphenoidal coordination geometry. The metal–Npyrazinedistances are much longer than the metal–Npyridinedistances; the difference is 0.389 (2) Å for the Cd—N bonds but only 0.286 (5) Å for the Hg—N bond lengths. In the crystals of both compounds, the polymer chains are linkedviapairs of C—H...Cl hydrogen bonds, forming corrugated slabs parallel to theacplane.


2015 ◽  
Vol 71 (10) ◽  
pp. 929-935 ◽  
Author(s):  
Hyun-Chul Kim ◽  
Ja-Min Gu ◽  
Seong Huh ◽  
Chul-Hyun Yo ◽  
Youngmee Kim

Two new one-dimensional CuIIcoordination polymers (CPs) containing theC2h-symmetric terphenyl-based dicarboxylate linker 1,1′:4′,1′′-terphenyl-3,3′-dicarboxylate (3,3′-TPDC), namelycatena-poly[[bis(dimethylamine-κN)copper(II)]-μ-1,1′:4′,1′′-terphenyl-3,3′-dicarboxylato-κ4O,O′:O′′:O′′′] monohydrate], {[Cu(C20H12O4)(C2H7N)2]·H2O}n, (I), andcatena-poly[[aquabis(dimethylamine-κN)copper(II)]-μ-1,1′:4′,1′′-terphenyl-3,3′-dicarboxylato-κ2O3:O3′] monohydrate], {[Cu(C20H12O4)(C2H7N)2(H2O)]·H2O}n, (II), were both obtained from two different methods of preparation: one reaction was performed in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) as a potential pillar ligand and the other was carried out in the absence of the DABCO pillar. Both reactions afforded crystals of different colours,i.e.violet plates for (I) and blue needles for (II), both of which were analysed by X-ray crystallography. The 3,3′-TPDC bridging ligands coordinate the CuIIions in asymmetric chelating modes in (I) and in monodenate binding modes in (II), forming one-dimensional chains in each case. Both coordination polymers contain two coordinated dimethylamine ligands in mutuallytranspositions, and there is an additional aqua ligand in (II). The solvent water molecules are involved in hydrogen bonds between the one-dimensional coordination polymer chains, forming a two-dimensional network in (I) and a three-dimensional network in (II).


2017 ◽  
Vol 1144 ◽  
pp. 173-180
Author(s):  
Pradhumna Mahat Chhetri ◽  
Yu-Chia Chang ◽  
Hui-Ling Hu ◽  
Yen-Hsun Chiang ◽  
Xiang-Kai Yang ◽  
...  

2019 ◽  
Vol 10 (1) ◽  
Author(s):  
Anton Vladyka ◽  
Mickael L. Perrin ◽  
Jan Overbeck ◽  
Rubén R. Ferradás ◽  
Víctor García-Suárez ◽  
...  

1999 ◽  
Vol 13 (09n10) ◽  
pp. 991-996
Author(s):  
M. Salvato ◽  
C. Attanasio ◽  
G. Carbone ◽  
T. Di Luccio ◽  
S. L. Prischepa ◽  
...  

High temperature superconducting multilayers have been obtained depositing Bi2Sr2CuO6+δ(2201) and ACuO2 layers, where A is Ca or Sr, by Molecular Beam Epitaxy (MBE) on MgO and SrTiO3 substrates. The samples, formed by a sequence of 2201/ACuO2 bilayers, have different thickness of ACuO2 layers while the thickness of the 2201 layers is kept constant. The surface structure of each layer has been monitored by in situ Reflection High Energy Electron Diffraction (RHEED) analysis which has confirmed a 2D nucleation growth. X-ray diffraction (XRD) analysis has been used to confirm that the layered structure has been obtained. Moreover, one-dimensional X-ray kinematic diffraction model has been developed to interpret the experimental data and to estimate the period of the multilayers. Resistive measurements have shown that the electrical properties of the samples strongly depend on the thickness of the ACuO2 layers.


1997 ◽  
Vol 52 (1) ◽  
pp. 125-134 ◽  
Author(s):  
Rolf W. Saalfrank ◽  
Roland Harbig ◽  
Oliver Struck ◽  
Frank Hampel ◽  
Eva Maria Peters ◽  
...  

Reaction of a methanolic copper(II) acetate solution with tetrazolyl enol derivatives 2a or 2b leads to the formation of the corresponding lD-coordination polymer 1∞[CuL2] 3a and pseudo 1D-coordination polymer [CuL2]2 3b, respectively. On the contrary, reaction of 2c with methanolic copper(II) acetate solution yields OH-bridged 1D-coordination polymer 1∞[CuL2(MeOH)2 3c. Single-crystal X-ray diffraction of the supramolecular species 3 established unequivocally the structures of the stairlike coordination compounds. Reaction of a methanolic copper(II) acetate solution with amidotetrazole derivative 6 leads to the formation of the lD-coordination polymer 1∞ [CuL2] 7. The structure of 7 has been established by X-ray structure analysis


Molecules ◽  
2021 ◽  
Vol 26 (17) ◽  
pp. 5400
Author(s):  
Roman D. Marchenko ◽  
Taisiya S. Sukhikh ◽  
Alexey A. Ryadun ◽  
Andrei S. Potapov

Coordination polymers with a new rigid ligand 1,3-bis(1,2,4-triazol-1-yl)adamantane (L) were prepared by its reaction with cadmium(II) or silver(I) nitrates. Crystal structure of the coordination polymers was determined using single-crystal X-ray diffraction analysis. Silver formed two-dimensional coordination polymer [Ag(L)NO3]n, in which metal ions are linked by 1,3-bis(1,2,4-triazol-1-yl)adamantane ligands, coordinated by nitrogen atoms at positions 2 and 4 of 1,2,4-triazole rings. Layers of the coordination polymer consist of rare 18- and 30-membered {Ag2L2} and {Ag4L4} metallocycles. Cadmium(II) nitrate formed two kinds of one-dimensional coordination polymers depending on the metal-to-ligand ratio used in the synthesis. Coordination polymer [Cd(L)2(NO3)2]n was obtained in case of a 1:2 M:L ratio, while for M:L = 2:1 product {[Cd(L)(NO3)2(CH3OH)]·0.5CH3OH}n was isolated. All coordination polymers demonstrated ligand-centered emission near 450 nm upon excitation at 370 nm.


2019 ◽  
Vol 75 (4) ◽  
pp. 422-432 ◽  
Author(s):  
Chao Bai ◽  
Bin Liu ◽  
Huai-Ming Hu ◽  
Jin-Dian Li ◽  
Xiaofang Wang ◽  
...  

Three series of lanthanide coordination polymers, namely catena-poly[[lanthanide(III)-μ2-(benzene-1,2-dicarboxylato)-μ2-[2-(2,2′:6′,2′′-terpyridin-4′-yl)benzoato]] monohydrate], {[Ln(C8H4O4)(C22H14N3O2)]·H2O} n or {[Ln(1,2-bdc)(L)]·H2O} n , with lanthanide (Ln) = dysprosium (Dy, 1), holmium (Ho, 2) and erbium (Er, 3), poly[bis(μ2-benzene-1,3-dicarboxylato)bis[μ2-2-(2,2′:6′,2′′-terpyridin-4′-yl)benzoato]dilanthanide(III)], [Ln2(C8H4O4)2(C22H14N3O2)2] n or [Ln2(1,3-bdc)2(L)2] n , with Ln = gadolinium (Gd, 4), Ho (5) and Er (6), and poly[(μ2-benzene-1,4-dicarboxylato)[μ2-2-(2,2′:6′,2′′-terpyridin-4′-yl)benzoato]lanthanide(III)], [Ln(C8H4O4)(C22H14N3O2)] n or [Ln(1,4-bdc)(L)] n , with Ln = Dy (7), Ho (8), Er (9) and ytterbium (Yb, 10), were synthesized under hydrothermal conditions and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Compounds 1–3 possess one-dimensional loop chains with Ln2(COO)2 units, which are extended into three-dimensional (3D) supramolecular structures by π–π interactions. Isostructural compounds 5 and 6 show 6-connected 3D networks, with pcu topology consisting of Ln2(COO)2 units. Compounds 7–10 display 8-connected 3D frameworks with the topological type rob, consisting of Ln2(COO)2 units. The influence of the coordination orientations of the aromatic dicarboxylate groups on the crystal structures is discussed.


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