Across the Dimensions: A Three‐Component Self‐Assembly of Pentaphosphaferrocene‐based Coordination Polymers

Abstract

Pentaphosphaferrocenes [Cp R Fe(η 5 -P 5 )] (Cp* = η 5 -C 5 Me 5 ) (A), Cp'' = η 5 -C 5 H 3 tBu 2 -1,3 (B)) are excellent building blocks for polymeric assemblies in supramolecular chemistry in combination with coinage metal salts of weakly coordinating anions such as AgSbF 6 . Adding rigid aromatic dinitriles ortho/meta/para-(NC) 2 C 6 H 4 in a one-pot reaction between [Cp R Fe(η 5 -P 5 )] and AgSbF 6 leads to various coordination polymers (CPs) by a three-component self-assembly. The sterical demand of the differently substituted cyclopentadiene ligands as well as the rigid constitution of the isomeric dinitriles (NC) 2 C 6 H 4 play a key role in the formation of the isolated CPs. All CPs were characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal Xray diffraction.

Potential of Mixed Dipnictogen Molybdenum Complexes in the Self-Assembly of Thallium Coordination Compounds

“…o-DFB and CD 2 Cl 2 were distilled from CaH 2 and other solvents were directly taken from an MBraun SPS-800 solvent purification system and degassed at room temperature prior to use. Solution 1 H (400.130 MHz), 11 B (128.379 MHz), 13 C (100.627 MHz), 19 F (376.498 MHz) and 31 P (161.976 MHz) NMR spectra were recorded on a Bruker Avance400 spectrometer using (H 3 C) 4 Si ( 1 H, 13 C), BF 3 •Et 2 O ( 11 B), CFCl 3 ( 19 F) or 85% phosphoric acid ( 31 P), respectively, as external standards. Chemical shifts (δ) are provided in parts per million (ppm) and coupling constants (J) are reported in Hertz (Hz).…”

“…Current approaches in supramolecular chemistry focus on the use of nitrogen-, oxygen-, and/or sulfur-containing organic linkers to connect different metal centers. − During the last decades, our group has demonstrated that organometallic E n (E = heavier group 15 element) ligand complexes are excellent building blocks for supramolecular assemblies as well . Indeed, many examples of the coordination chemistry of E n ( n = 1–6) ligand complexes toward coinage metal salts, also in combination with organic linkers, were reported during the past two decades. , This novel approach allowed the synthesis of a large library of aggregates including polymeric (1D, − 2D , and 3D coordination polymers) and discrete (monomeric, dimeric or spherical aggregates − as well as nanobowls) supramolecular assemblies. While the coinage metal salts of Cu I /Ag I /Au I have already been extensively utilized in these studies, the monovalent ions of the heavier group 13 elements, namely In I and Tl I , have only recently attracted general interest within the field of supramolecular chemistry.…”

“… 5 Indeed, many examples of the coordination chemistry of E n ( n = 1–6) ligand complexes toward coinage metal salts, also in combination with organic linkers, were reported during the past two decades. 6 , 7 This novel approach allowed the synthesis of a large library of aggregates including polymeric (1D, 8 − 10 2D 11 , 12 and 3D 13 coordination polymers) and discrete (monomeric, 14 dimeric 15 or spherical aggregates 16 − 18 as well as nanobowls 19 ) supramolecular assemblies. While the coinage metal salts of Cu I /Ag I /Au I have already been extensively utilized in these studies, the monovalent ions of the heavier group 13 elements, namely In I and Tl I , have only recently attracted general interest within the field of supramolecular chemistry.…”