Solid-state dynamics and single-crystal to single-crystal structural transformations in octakis(3-chloropropyl)octasilsesquioxane and octavinyloctasilsesquioxane

2017 ◽  
Vol 19 (40) ◽  
pp. 27516-27529 ◽  
Author(s):  
A. Kowalewska ◽  
M. Nowacka ◽  
M. Włodarska ◽  
B. Zgardzińska ◽  
R. Zaleski ◽  
...  
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Structural Transformations ◽  
Crystal Lattices ◽  
Thermally Induced ◽  
Crystal Structural

Thermally induced formation of symmetric crystal lattices in functional POSS proceeds via different mechanisms and results in unique reversible phenomena.

scholarly journals Thermal Reactivity in Metal Organic Materials (MOMs): From Single-Crystal-to-Single-Crystal Reactions and Beyond

Materials ◽  
2019 ◽  
Vol 12 (24) ◽  
pp. 4088
Author(s):  
Javier Martí-Rujas
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Organic Materials ◽  
Structural Transformations ◽  
Atomic Motion ◽  
X Ray Diffraction ◽  
Thermally Induced ◽  
X Ray ◽  
Thermal Reactivity ◽  
Metal Organic

Thermal treatment is important in the solid-state chemistry of metal organic materials (MOMs) because it can create unexpected new structures with unique properties and applications that otherwise in the solution state are very difficult or impossible to achieve. Additionally, high-temperature solid-state reactivity provide insights to better understand chemical processes taking place in the solid-state. This review article describes relevant thermally induced solid-state reactions in metal organic materials, which include metal organic frameworks (MOFs)/coordination polymers (CPs), and second coordination sphere adducts (SSCs). High temperature solid-state reactivity can occur in a single-crystal-to-single crystal manner (SCSC) usually for cases where there is small atomic motion, allowing full structural characterization by single crystal X-ray diffraction (SC-XRD) analysis. However, for the cases in which the structural transformations are severe, often the crystallinity of the metal-organic material is damaged, and this happens in a crystal-to-polycrystalline manner. For such cases, in the absence of suitable single crystals, structural characterization has to be carried out using ab initio powder X-ray diffraction analysis or pair distribution function (PDF) analysis when the product is amorphous. In this article, relevant thermally induced SCSC reactions and crystal-to-polycrystalline reactions in MOMs that involve significant structural transformations as a result of the molecular/atomic motion are described. Thermal reactivity focusing on cleavage and formation of coordination and covalent bonds, crystalline-to-amorphous-to-crystalline transformations, host–guest behavior and dehydrochlorination reactions in MOFs and SSCs will be discussed.

Thermally Triggered Solid-State Single-Crystal-to-Single-Crystal Structural Transformation Accompanies Property Changes

2015 ◽  
Vol 21 (12) ◽  
pp. 4703-4711 ◽  
Author(s):  
Quan-Quan Li ◽  
Chun-Yan Ren ◽  
Yang-Yang Huang ◽  
Jian-Li Li ◽  
Ping Liu ◽  
...  
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Structural Transformation ◽  
Crystal Structural ◽  
Property Changes ◽  
Thermally Triggered

Iron(II) and Nickel(II) Complexes of 2,6-Di(Thiazol-4-Yl)Pyridine and Related Ligands: Magnetic, Spectral and Structural Studies

1986 ◽  
Vol 39 (2) ◽  
pp. 209 ◽  
Author(s):  
AT Baker ◽  
HA Goodwin
Keyword(s):  
Solid State ◽  
Metal Complexes ◽  
Single Crystal ◽  
Coordination Sphere ◽  
Structural Parameters ◽  
Complex Cation ◽  
Magnetic Behaviour ◽  
Structural Studies ◽  
Thermally Induced ◽  
X Ray

2,6-Di(thiazol-4-yl)pyridine (1a), 2,6-di(2-methylthiazol-4-yl)pyridine (1b) and 2,6-di(2-phenylthiazol-4-yl)pyridine (1c) have been prepared by Hantzsch syntheses from 2,6-di(ω- bromoacetyl )pyridine and the appropriate thioamide. Bis ( ligand ) iron(II) and nickel(II) complexes of (1a) and (1b) have been prepared but no metal complexes of (1c) were isolated. The bis ( ligand ) iron(II) complexes of (1a) are low-spin whereas those of (1b) undergo thermally induced spin-transitions, both in the solid state and solution. The field strengths of the ligands , determined from the spectra of their nickel(II) complexes, correlate well with the observed magnetic behaviour of their iron(II) complexes. The structure of [FeL2][ClO4]2.H2O, L = (1a), was determined by single-crystal X-ray diffractometry . The complex cation has the meridional configuration with the ligand functioning as an approximately planar tridentate. The structural parameters relating to the Fe-N6 coordination sphere are remarkably similar to those found for bis (2,2′:6′, 2′- terpyridine )iron(II) bis ( perchlorate ) monohydrate.

Variable-temperature structural studies on valence tautomerism in cobalt bis(dioxolene) molecular complexes

2017 ◽  
Vol 73 (2) ◽  
pp. 304-312 ◽  
Author(s):  
Venkatesha R. Hathwar ◽  
Marian Stingaciu ◽  
Bo Richter ◽  
Jacob Overgaard ◽  
Bo B. Iversen
Keyword(s):  
Single Crystal ◽  
Variable Temperature ◽  
Molecular Complexes ◽  
Structural Studies ◽  
Coordination Environment ◽  
Valence Tautomerism ◽  
Thermally Induced ◽  
Transition Mechanism ◽  
Crystal Structural ◽  
Cobalt Coordination

A variable-temperature single-crystal structural study of five valence tautomeric cobalt molecular complexes, CoII(3,5-DBSQ)2(DBPy)2(1), CoII(3,5-DBSQ)2(DBPy)2·1.33C7H8(1S), CoII(3,5-DBSQ)2(DCPy)2·C7H8(2S), CoII(3,5-DBSQ)2(TBPy)2(3) and CoII(3,5-DBSQ)2(TCPy)2(4) (S = toluene, 3,5-DBSQ = 3,5-di-tert-butylsemiquinonate, DBPy = 3,5-dibromopyridine, DCPy = 3,5-dichloropyridine, TBPy = 3,4,5-tribromopyridine and TCPy = 3,4,5-trichloropyridine) is reported. The re-crystallization of (1S) in toluene at 277 K resulted in a concomitant formation of a solvent-free polymorph, CoII(3,5-DBSQ)2(DBPy)2(1). Thermally induced valence tautomerism (VT) is observed only in (1S), (1) and (2S) [hs-CoII(3,5-DBSQ)2L2↔ ls-CoIII(3,5-DBSQ)(3,5-DBCat)L2(hs = high spin, ls = low spin, 3,5-DBCat = 3,5-di-tert-butylcatecholate)], whereas (3) and (4) remain locked in the hs-CoII(3,5-DBSQ)2state during cooling of the sample. Multi-temperature single-crystal studies demonstrate the change in cobalt coordination environment during the VT conversion. The non-solvated compound (1) shows a sharp VT transition (T1/2∼ 245 K with ΔT∼ 10 K) from hs-CoII(3,5-DBSQ)2(DBPy)2to ls-CoIII(3,5-DBSQ)(3,5-DBCat)(DBPy)2oxidation state, whereas the other polymorph with lattice solvent (1S) results in a broad transition (T1/2∼ 150 K with ΔT∼ 100 K). This increase in the VT transition temperature for (1) relative to (1S) illustrates the effect of lattice solvent on the VT transition mechanism. Additionally, the influence of halogen substitutions on the pyridine ring is discussed with respect to observed VT behaviour in the studied compounds.

Group 6 Metal Mixed Carbonyl Complexes with a Carboxyferrocenylphosphane

2000 ◽  
Vol 65 (12) ◽  
pp. 1897-1910 ◽  
Author(s):  
Lenka Lukešová ◽  
Jiří Ludvík ◽  
Ivana Císařová ◽  
Petr Štěpnička
Keyword(s):  
Carbon Monoxide ◽  
Cyclic Voltammetry ◽  
Solid State ◽  
Single Crystal ◽  
Carbonyl Complexes ◽  
State Structure ◽  
X Ray Diffraction ◽  
Thermally Induced ◽  
X Ray ◽  
Ferrocenecarboxylic Acid

A series of complexes [M(CO)5(Hdpf-κP)], where M = Cr (1), Mo (2) and W (3), and Hdpf is 1'-(diphenylphosphanyl)ferrocenecarboxylic acid, was obtained by thermally-induced (2) or photochemically-assisted (1, 3) displacement of carbon monoxide with Hdpf from the corresponding hexacarbonyl complexes. The complexes were characterized by NMR, UV-VIS and IR spectroscopies and further studied by cyclic voltammetry. The solid-state structure of complex 1 has been determined by single-crystal X-ray diffraction.

Iron(II) and Nickel(II) Complexes of 4,4′-Bithiazole: Spectral, Magnetic and Structural Studies

1985 ◽  
Vol 38 (6) ◽  
pp. 851 ◽  
Author(s):  
AT Baker ◽  
HA Goodwin
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Bond Length ◽  
Least Squares ◽  
State Transitions ◽  
Structural Studies ◽  
Octahedral Structure ◽  
Thermally Induced ◽  
X Ray ◽  
Distorted Octahedral

Iron(II) and nickel(II) complexes of 4,4′-bithiazole (L) have been prepared. Salts of [FeL3]2+ undergo thermally induced spin-state transitions, in the solid state and in solution. The structures of both [FeL3] [ClO4]2 and [NiL3] [ClO4]2 have been determined by single-crystal X-ray diffractometry . The compounds are isomorphous : monoclinic with space group C2/c, with four molecules in a unit cell of dimensions (Fe, Ni): a 17.250(3), 17.379(3); b 9.8168(9), 9.685(1); c 16.867(3), 17.135(3) Ǻ; β 105.943(7), 104.860(7)°. The structures were refined by least-squares methods to residuals of 0.033 (Fe) and 0.033 (Ni) for 1917 (Fe) and 2017 (Ni) observed reflections. The cations have a distorted octahedral structure with the average Ni-N bond length being 0.11 Ǻ longer than the average Fe-N bond length.

New hybrid organic-zincophosphate frameworks: single-crystal-to-single-crystal structural transformation and remarkable thermal and chemical stabilities

2016 ◽  
Vol 45 (17) ◽  
pp. 7231-7234 ◽  
Author(s):  
Tsung-Yuan Chang ◽  
Zhao-Nan Yan ◽  
Chun-Chi Wang ◽  
Hsing-Chun Li ◽  
Hsiu-Mei Lin ◽  
...  
Keyword(s):  
Single Crystal ◽  
Structural Transformation ◽  
Structural Transformations ◽  
Metal Phosphates ◽  
Crystal Structural

This research is the first example of hybrid metal phosphates that undergo SCSC structural transformations and exhibit remarkable thermal and chemical stabilities.

scholarly journals Hydrogen-Bonding Assembly of Coordination Polymers Showing Reversible Dynamic Solid-State Structural Transformations

Inorganics ◽  
2018 ◽  
Vol 6 (4) ◽  
pp. 115
Author(s):  
Hitoshi Kumagai ◽  
Sadahiro Yagishita ◽  
Ken Kanazashi ◽  
Mariko Ishii ◽  
Shinya Hayami ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Structural Transformation ◽  
Coordination Polymers ◽  
Chain Structure ◽  
Structural Transformations ◽  
The Other ◽  
Ambient Conditions ◽  
Thermally Induced ◽  
Dehydration Processes

We herein report the synthesis, single-crystal structures of coordination polymers, and structural transformations of complexes employing 1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile (tdpd2−) and pyrazine (pyz) as bridging ligands. {[M(H2O)4(pyz)][M(tdpd)2(pyz)]·6(H2O)}n, [1·10H2O and 2·10H2O where M = Co (1) and Zn (2)], consists of two types of crystallographically independent one-dimensional (1D) structures packed together. One motif, [M(tdpd)2(pyz)]2− (A), is an anionic infinite pyz bridged 1D array with chelating tdpd2− ligands, and the other motif is a cationic chain, [M(H2O)4(pyz)]2+ (B), which is decorated with four terminal water molecules. The 1D arrays (A) and (B) are arranged in parallel by multi-point hydrogen-bonding interactions in an alternate (A)(B)(A)(B) sequence extending along the c-axis. Both compounds exhibit structural transformations driven by thermal dehydration processes around 350 K to give partially dehydrated forms, 1·2H2O and 2·2H2O. The structural determination of the partially dehydrated form, 2·2H2O, reveals a solid-state structural transformation from a 1D chain structure to a two-dimensional (2D) coordination sheet structure, [Zn2(tdpd)2(H2O)2(pyz)]n (2·2H2O). Further heating to 500 K yields the anhydrous form 2. While the virgin samples of 1·10H2O and 2·10H2O crystallize in different crystal systems, powder X-ray diffraction (PXRD) measurements of the dehydrated forms, 1·2H2O and 2·2H2O, are indicative of the same structure. The structural transformation is irreversible for 1·10H2O at ambient conditions. On the other hand, compound 2·10H2O shows a reversible structural change. The solid-state structural transformation for 1·10H2O was also confirmed by monitoring in-situ magnetic susceptibility, which is consistent with other thermally-induced measurements.

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