New Organotin/CuCN/Quinazoline 3D-Supramolecular Coordination Polymers Having Catalytic and Luminescence Activities

Abstract

The new bimetallic supramolecular coordination polymers (SCP); 3 ∞ [Cu(CN) 2 ·Me 3 Sn·qaz], 1 and 3 ∞ [Cu 2 (CN) 4 ·(Ph 3 Sn) 2 ·qaz], 2 (qaz = quinazoline), are prepared in water/acetonitrile solvent at room temperature. The structure of 1 consists of the anionic Cu(CN) 2 building blocks connected by the Me 3 Sn cations to form zigzag chains which are bridged by qaz creating 2D-sheets. The interwoven infinite sheets are arranged in parallel A···A···A fashion developing 3D-network structure via H-bonds, π-π stacking, and Cu-C contacts. The network structure of 2 exhibits two different copper sites forming two Cu(CN) 2 building blocks which are connected by the Ph 3 Sn groups constructing elongated corrugated chains. The qaz ligand connects these chains forming 3D-network structure containing the rhombic [Cu 2 (μ 3 -CN) 2 ] motif. 1 and 2 are luminescent materials which can be used in applications as molecular sensing systems. Also, the catalytic activity of 1 and 2 was investigated towards the degradation of Metanil Yellow (MY) dye by dilute solution of hydrogen peroxide as oxidant.

Structure and Catalytic Activity of New Metal‐Organic Frameworks Based on Copper Cyanide and Quinoline Bases

“…[40,43] However, the MOF [Cu(CN) 2 · Me 3 Sn·qaz] a prototype SCP containing the qaz molecule, synthesized using similar adducts and reaction conditions, exhibits a (Sn/Cu) ratio of 1:1. [26] Its structure resembles that of 2. It consists of anionic Cu(CN) 2 building blocks connected by Me 3 Sn cations to form zigzag chains, which are bridged by qaz creating 2D sheets.…”

“…The interwoven infinite sheets are arranged in parallel fashion developing a 3D network structure by hydrogen bonds, π-π stacking, and Cu-C contacts. [26] MOFs 1 and 2 can be used as heterogeneous catalysts for the oxidative discoloration of MB by a diluted solution of hydrogen peroxide as oxidant. The presence of organic contaminants including dyes in wastewater has been an important problem in many countries since the textile industry has been widely developed.…”

“…[14,18,20] Furthermore, R 3 Sn + cations have a good capability of bridging CuCN fragments to produce a limited number of 3D frameworks. [5,25,26] Single crystal studies for a number of CuCN complexes with nitrogen bases forming different structures have been pre-of the chain. Hydrogen bonds play an essential role for the construction of the 3D network structure.…”

3D-Interpenetrating Frameworks of 3∞[Cu2(CN)4(Me3Pb)2(bpy)] Containing the Rhombic [Cu2(µ3-CN)2] Motifs

“…cations (R = Me or Ph) [1][2][3][4][5][6]. Because a single cyanide ligand can bridge two, three, or even four metal centers, it serves as an excellent network former.…”

“…However, the structure features of these SCP are the formation of 3D-networks which contain the rhombic [Cu 2 (l 3 -CN) 2 ] motif or strong Cu…Cu interaction, even shorter than in elemental copper, via interwoven of the sheets [7][8][9]. Such porous networks have potential applications in areas such as separations, gas storage, antitumor, luminescence and catalysis [5,[10][11][12]. In addition, highly luminescent metal-organic materials might be used in sensing systems when molecular absorption of small molecules leads to an alteration in network luminescence behavior [13][14][15][16].…”