Neutral two-dimensional organometallic–organic hybrid polymers based on pentaphosphaferrocene, bipyridyl linkers and CuCl

Abstract

The reaction of the P ligand complex [Cp*Fe(η-P)] (1: Cp* = η-CMe) with CuCl in the presence of 4,4'-bipyridine or 1,2-di(4-pyridyl)ethylene leads to the formation of three unprecedented neutral 2D organometallic-organic hybrid networks, the constitutional isomers [CuCl{Cp*Fe(μ,η-P)}(μ,η-CHN)] (2 and 3) and the coordination polymer [(CuCl){Cp*Fe(μ,η-P)}(μ,η-CHN)] (4) with isomeric square (2 and 3) and honeycomb (4) layer topologies.

The Diphosphorus Complex [Cp2Cr2(CO)4(η2‐P2)] as a Building Block in the Coordination Chemistry of Silver

“…Parallel to our previous well‐developed method involving bipyridyl linker together with metal salts and iron‐ or molybdenum‐based P n ligand complexes, the use of 1,4‐dicyanobenzene together with Ag I and a chromium‐based P 2 ligand complex allows access to an unprecedented 1D organometallic‐organic hybrid CP, and opens a new chapter in this field of supramolecular chemistry by using a nitrile linker. These new results, in addition to the large variety of assemblies based on the ligand 1 , show the advantage of our approach using P‐donating ligand complexes in metal‐directed self‐assembly, which will lead to a very rich and original library of supramolecular compounds. Current investigations involve reactions based on the phosphorus‐rich P n ligand complexes ( n = 3, 4, 5) to study the possibility of utilizing these rarely used ligands in similar three‐component reactions leading to valuable phosphorus‐rich organometallic‐organic hybrid materials.…”

“…This novel method allows the synthesis of 1D, 2D or even 3D coordination polymers (CPs), giant fullerene‐like inorganic spherical aggregates and organometallic nanosized capsules . Recently, an additional interest in these organometallic ligand complexes emerged, as, for example, the tetrahedrane complex [Cp 2 Mo 2 (CO) 4 (η 2 ‐P 2 )] (Cp = C 5 H 5 ) ( 1 ) was used in a mixed‐ligand reaction together with Ag I or Cu I salts and ditopic pyridine‐based linkers to form unprecedented organometallic‐organic hybrid CPs . Our interest in investigating the possibility to design a new class of hybrid CPs was therefore sparked.…”

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

“…Thus, the subtle change in coordination modes of organic ligand resulted in the formation of this polymeric structure shown in Figure 16. 171 An unprecedented organometallic pentaphosphaferrocenebased 2D MOF [Cu 2 Cl 2 {Cp*Fe(μ 3 ,η 5:1:1 -P 5 )}(μ,η 1 :1-C 10 H 8 N 2 )] representing rectangular grid structure has been reported by Scheer et al 172 It consists of large and small rectangular rings with maximum dimensions 1.14 and 1.51 nm, respectively, comprises two [Cu 2 Cl 2 ] four-membered rings bridged by a pentaphosphaferrocene molecule with the cyclo-P 5 ligand adopting 1,3-bridging mode (Figure 17). On the contrary, its constitutional isomer exhibits trapezoidal rings.…”

“…2D neutral polymeric framework of [Cu 2 Cl 2 {Cp*Fe­(μ 3 ,η 5:1:1 -P 5 )}­(μ,η 1 :1-C 10 H 8 N 2 )]. Reproduced with permission from ref . Copyright 2018 Royal Society of Chemistry.…”

The Triple-Decker Complex [Cp*Fe(µ,η5:η5-P5)Mo(CO)3] as a Building Block in Coordination Chemistry

“…With Cu I halides and 1 , depending on the reaction conditions, a set of one- and two-dimensional coordination polymers [9,10], fascinating fullerene-like spherical aggregates [11,12,13,14,15,16] as well as an organometallic nanosized capsule [17] are accessible. Moreover, when ditopic organic linkers are added to 1 and Cu I halides, unprecedented organometallic–organic hybrid polymers with various dimensionalities can be realized [18,19].…”