scholarly journals Halide metathesis in overdrive: mechanochemical synthesis of a heterometallic group 1 allyl complex

2019 ◽  
Vol 15 ◽  
pp. 1856-1863 ◽  
Author(s):  
Ross F Koby ◽  
Nicholas R Rightmire ◽  
Nathan D Schley ◽  
Timothy P Hanusa ◽  
William W Brennessel
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Alkali Metal ◽  
Driving Forces ◽  
Metal Exchange ◽  
Heterometallic Complex ◽  
Metal Centers ◽  
Allyl Complex ◽  
Site Disorder ◽  
Group 1

As a synthesis technique, halide metathesis (n RM + M'X n → R n M' + n MX) normally relies for its effectiveness on the favorable formation of a metal halide byproduct (MX), often aided by solubility equilibria in solution. Owing to the lack of significant thermodynamic driving forces, intra-alkali metal exchange is one of the most challenging metathetical exchanges to attempt, especially when conducted without solvent. Nevertheless, grinding together the bulky potassium allyl [KA']∞ (A' = [1,3-(SiMe3)2C3H3]–) and CsI produces the heterometallic complex [CsKA'2]∞ in low yield, which was crystallographically characterized as a coordination polymer that displays site disorder of the K+ and Cs+ ions. The entropic benefits of mixed Cs/K metal centers, but more importantly, the generation of multiple intermolecular K…CH3 and Cs…CH3 interactions in [CsKA'2]∞, enable an otherwise unfavorable halide metathesis to proceed with mechanochemical assistance. From this result, we demonstrate that ball milling and unexpected solid-state effects can permit seemingly unfavored reactions to occur.

A novel multichromic Zn (Ⅱ) cationic coordination polymer based on a new flexible viologen ligand exhibiting aniline detection in solid state

2021 ◽  
Author(s):  
Jiayun Zou ◽  
jie Ji ◽  
Meihong Fan ◽  
Jiayu Li ◽  
Haiyu Wang ◽  
...  
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Pyromellitic Acid

In this paper, a novel multichromic catioic coordination polymer, named [Zn4 (BTC)3(bcbpy)2] ·5H2O (1) based on a new flexible viologen ligand 1,1'-bis(3-cyanobenzyl)-[4,4'-bipyridine-1,1'-diium (H2bcbpy·2Cl), Zn(NO3)2·6H2O and pyromellitic acid (H4BTC), was synthesized....

scholarly journals Proton-conductive coordination polymer glass for solid-state anhydrous proton batteries

2021 ◽  
Vol 12 (16) ◽  
pp. 5818-5824
Author(s):  
Nattapol Ma ◽  
Soracha Kosasang ◽  
Atsushi Yoshida ◽  
Satoshi Horike
Keyword(s):  
Mechanical Properties ◽  
Solid State ◽  
Coordination Polymer ◽  
Proton Battery ◽  
Polymer Glass

Melt-quenched coordination polymer glass shows exclusive H+ conductivity (8.0 × 10−3 S cm−1 at 120 °C, anhydrous) and optimal mechanical properties (42.8 Pa s at 120 °C), enables the operation of an all-solid-state proton battery from RT to 110 °C.

scholarly journals Iron(II) complexes of dimethyltriazacyclophane

2018 ◽  
Vol 74 (12) ◽  
pp. 1641-1649
Author(s):  
Wei-Tsung Lee ◽  
Matthias Zeller ◽  
David Upp ◽  
Yuliya Politanska ◽  
Doug Steinman ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Solid State ◽  
Dft Calculations ◽  
Density Functional Calculations ◽  
Density Functional ◽  
Coordination Mode ◽  
Functional Theory ◽  
Metal Centers ◽  
Bonding Interaction

Treatment of the ortho-triazacyclophane 1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-triene [(C6H5)3(NH)(NCH3)2, L1] with Fe[N(SiMe3)2]2 yields the dimeric iron(II) complex bis(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)bis[(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido)iron(II)], [Fe(C20H18N3)4] or Fe2(L1)4 (9). Dissolution of 9 in tetrahydrofuran (THF) results in solvation by two THF ligands and the formation of a simpler monoiron complex, namely bis(μ-1,4-dimethyltribenzo[b,e,h][1,4,7]triazacyclonona-2,5,8-trien-7-ido-κN 7)bis(tetrahydrofuran-κO)iron(II), [Fe(C20H18N3)2(C4H8O)2] or (L1)2Fe(THF)2 (10). The reaction is reversible and 10 reverts in vacuo to diiron complex 9. In the structures of both 9 and 10, the monoanionic triazacyclophane ligand L1− is observed in only the less-symmetric saddle conformation. No bowl-shaped crown conformers are observed in the solid state, thus preventing chelating κ3-coordination to the metal as had been proposed earlier based on density functional theory (DFT) calculations. Instead, the L1− ligands are bound in either a η2-chelating fashion through the amide and one amine donor (for one of the four ligands of 9), or solely through their amide N atoms in an even simpler monodentate η1-coordination mode. Density functional calculations on dimer 9 revealed nearly full cationic charges on each Fe atom and no bonding interaction between the two metal centers, consistent with the relatively long Fe...Fe distance of 2.912 (1) Å observed in the solid state.

Influence of Alkali Metal Cations on the Photodimerization of Bromo Cinnamates Studied by Solid-State NMR

2020 ◽  
Vol 124 (50) ◽  
pp. 27614-27620
Author(s):  
Marufa Zahan ◽  
He Sun ◽  
Sophia E. Hayes ◽  
Harald Krautscheid ◽  
Jürgen Haase ◽  
...  
Keyword(s):  
Solid State ◽  
Alkali Metal ◽  
Solid State Nmr ◽  
Metal Cations ◽  
Alkali Metal Cations

A paramagnetic Cu(i)/Cu(ii)/Zn(ii) coordination polymer with multiple CN-binding modes and its solid-state NMR characterization

2006 ◽  
pp. 744 ◽  
Author(s):  
Liang Ouyang ◽  
Pedro M. Aguiar ◽  
Raymond J. Batchelor ◽  
Scott Kroeker ◽  
Daniel B. Leznoff
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
Solid State Nmr ◽  
Binding Modes ◽  
Nmr Characterization

Synthesis of New Chalcogenide Materials. The Novel One-Dimensional Semiconductor K4 Ti3 S14

1987 ◽  
Vol 97 ◽  
Author(s):  
Steven A. Sunshine ◽  
Doris Kang ◽  
James A. Ibers
Keyword(s):  
Electrical Conductivity ◽  
Solid State ◽  
Alkali Metal ◽  
The Novel ◽  
Conductivity Measurements ◽  
One Dimensional ◽  
General Utility ◽  
Solid State Materials ◽  
Chalcogenide Materials

ABSTRACTThe use of A2 Q/Q melts (A - alkali metal, Q - S or Se) for the synthesis of new one-dimensional solid-state materials is found to be of general utility and is illustrated here for the synthesis of K4 Ti3 SI4. Reaction of Ti metal with a K2 S/S melt at 375°C for 50 h affords K4 Ti3 SI4. The structure possesses one-dimensional chains of seven and eightcoordinate Ti atoms with each chain isolated from all others by surrounding K atoms. There are six S-S pairs (dave - 2.069(3) Å) so that the compound is one of TiIV and may be described as K4 [Ti3 (S)2 (S2)6]. Electrical conductivity measurements indicate that this material is a semiconductor.

Synthesis and structural characterization of a magnesium phthalocyanine(3–) anion

2012 ◽  
Vol 16 (01) ◽  
pp. 154-162 ◽  
Author(s):  
Edwin W.Y. Wong ◽  
Daniel B. Leznoff
Keyword(s):  
Absorption Spectrum ◽  
Solid State ◽  
Single Crystal ◽  
Structural Characterization ◽  
Heterometallic Complex ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography

The reduction of magnesium phthalocyanine (MgPc) with 2.2 equivalents of potassium graphite in 1,2-dimethoxyethane (DME) gives [K2(DME)4]PcMg(OH)(1) in 67% yield. Compound 1 was structurally characterized using single crystal X-ray crystallography and was found to be a monomeric, heterometallic complex consisting of a μ3-OH ligand that bridges a [MgIIPc3-]- anion to two potassium cations solvated by four DME molecules. An absorption spectrum of 1 confirms the Pc ligand is singly reduced and has a 3–charge. The solid-state structure of 1 does not indicate breaking of the aromaticity of the Pc ligand. Compound 1 is only the second Pc3- complex and the first reduced MgPc to be isolated and structurally characterized.

Ibuprofen as linker for calcium(II) in a 1D-coordination polymer: a solid state investigation complemented with solution studies

2021 ◽  
pp. 120319
Author(s):  
Juliana Morais Missina ◽  
Luca Conti ◽  
Patrizia Rossi ◽  
Andrea Ienco ◽  
Giovana Gioppo Nunes ◽  
...  
Keyword(s):  
Solid State ◽  
Coordination Polymer ◽  
1D Coordination Polymer ◽  
Solution Studies
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