Synthesis and Characterization of the Mixed‐Linker Copper(II) Coordination Polymer [Cu(HO₃PC₆H₄SO₃)(C₁₀N₂H₈)]·H₂O

Abstract

A new copper(II) phosphonatobenzenesulfonate incorporating 4,4'-bipyridine (4,4'-bipy) as auxiliary ligand has been discovered through systematic high-throughput (HT) screening of the system Cu(NO 3 ) 2 ·3H 2 O/H 2 O 3 PC 6 H 4 SO 3 H/4,4'-bipy using different solvents. The hydrothermal synthesis of [Cu(HO 3 PC 6 H 4 SO 3 )(C 10 H 8 N 2 )]·H 2 O (1) was further optimized by screening various copper(II) salts. The crystal structure of 1 was determined by single-crystal X-ray diffraction and unveiled the presence of isolated sixfold coordinated Jahn-Teller-distorted Cu 2+ ions. The isolated CuN 2 O 4 octahedra are interconnected by phosphonate and sulfonate groups to form chains along the c-axis. The organic groups, namely phenyl rings and 4,4'-bipy molecules cross-link the chains into a three-dimensional framework. Water

Five New Coordination Polymers with a Bifunctional Phosphonate‐Sulfonate Linker Molecule

“…acids [7][8][9][10][11][12][13][14][15][16][17][18] or rigid m-or p-phosphonobenzenesulfonic acid. [19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] First studies on 2-phosphonoethanesulfonic and 4-phosphonobutanesulfonic acids were carried out in the group of Alberti et al [7] Subsequently, high-throughput investigations allowed to identify fields of product formation and to establish synthesis-structure relationships of a variety of new CPs. [9][10][11][12][13][14]16,17] In addition, in situ X-ray diffraction studies were carried out to study the crystallization process in detail.…”

“…These compounds can be of great interest, particularly in the field of proton conduction, since due to the presence of mobile protons in the form of hydrogenphosphonate groups and water molecules in the crystal structure, defined proton conduction paths can be formed . However, there are only a few examples of CPs containing simultaneously sulfonate and phosphonate functions on the same linker molecule . The majority of such CPs have been obtained using flexible phosphonoalkylsulfonic acids or rigid m ‐ or p ‐phosphonobenzenesulfonic acid .…”

“…However, there are only a few examples of CPs containing simultaneously sulfonate and phosphonate functions on the same linker molecule . The majority of such CPs have been obtained using flexible phosphonoalkylsulfonic acids or rigid m ‐ or p ‐phosphonobenzenesulfonic acid . First studies on 2‐phosphonoethanesulfonic and 4‐phosphonobutanesulfonic acids were carried out in the group of Alberti et al Subsequently, high‐throughput investigations allowed to identify fields of product formation and to establish synthesis‐structure relationships of a variety of new CPs , .…”

“…These CPs were mostly investigated for their structural features and spectroscopic characteristics. p ‐Phosphonobenzenesulfonic acid was successfully employed in the synthesis of Cu 2+ ‐,, , Ti 4+ ‐, and Zr 4+ ‐containing CPs.…”

New copper aryl phosphonates with auxiliary nitrogen ligands

“…4-Sulfophenylphosphonic acid represents a ligand that has been used in the synthesis of metal phosphonates only recently; namely, it was employed in the syntheses of four new copper sulfophenylphosphonates 27 and one copper sulfophenylphosphonate in which 4,4 0 -bipyridine served as an auxiliary bridging ligand. 28 The reason for this is the difficulty in its preparation, which has been resolved only lately. 29,30…”