Nitrogen-Based Linkers with a Mesitylene Core: Synthesis and Characterization

Abstract

Mesitylene was used as a core in seven new tritopic nitrogen containing linkers. Three of the linkers, each containing three nitrile groups, were obtained through Suzuki, Sonogashira and Heck-type coupling reactions. Next, these were converted to tetrazol-5-yl moieties by the cycloaddition of sodium azide to the nitrile functionalities. The last linker, containing three 1,2,3-triazol-4-yl moieties, was synthesized by the Huisgen cycloaddition of phenyl azide to the corresponding alkyne. The latter was obtained via a Corey–Fuchs reaction sequence from the previously reported formyl derivative. As the proof of concept for their potential in MOF design, one of the nitriles was used to build an Ag-based network.

Synthesis of New Zinc and Copper Coordination Polymers Derived from Bis (Triazole) Ligands

“…The remaining two nitrogen atoms resonate at 350 and 360 ppm, as obtained from three-bond correlations with butyl CH 2 protons and triazole CH proton, respectively. These nitrogen chemical shifts values are similar to previously reported 15 N and 14 N chemical shifts for other 1,2,3-triazole compounds [28].…”

“…Signals assignments are annotated on the figure; Figure S5: H,H-NOESY spectrum recorded for compound L 1 , with the insert showing the NOE correlation signals between 1,2,3-triazole proton and methoxy and butyl protons; Figure S6: Detailed spectral region of 1 H, 15 N-HMBC spectrum corresponding to compound L 1 , showing the proton-nitrogen two and three bonds couplings used to determine the chemical shifts values for nitrogen atoms; Figure S7: 1 H-NMR spectrum corresponding to compound L 2 , recorded in CDCl 3 , at 600.1 MHz. Signals assignments are annotated on the figure; Figure S8: 13 C-NMR spectrum corresponding to compound L 2 , recorded in CDCl 3 , at 100.6 MHz; Figure S9: Detailed spectral region of 1 H, 15 N-HMBC spectrum corresponding to compound L 2 , showing the proton-nitrogen two and three bounds couplings used to determine the chemical shifts values for nitrogen atoms; Figure S10: 1 H-NMR spectrum corresponding to bisazide 2, recorded in CDCl 3 , at 600.1 MHz. Signals assignments are annotated on the figure; Figure S11: 13 C-NMR spectrum corresponding to bisazide 2, recorded in CDCl 3 , at 100.6 MHz; Figure S12: Overlapped 1 H-NMR spectra recorded at 400.1 MHz, in DMSO-d 6 , for free L 1 (a), [ZnL 1 (NO 3 ) 2 ] n complex (b) and [CuL 1 (NO 3 ) 2 ] n complex (c).…”

“…Because polynitrogen ligands have multicoordination sites, they thus a wide range of potential coordination modes with the metal ions, so it is feasible to create crystals with a variety of pores and channels that can generate interesting physicochemical and/or biological features [13]. Known to act as dinucleating or trinucleating ligands, substituted 1,2,3-triazole derivatives are a significant class of N-donors commonly utilized in the assembly of coordination polymers, mainly due to their outstanding coordination capabilities and high versatility [12,[14][15][16]. These fivemember heterocyclic derivatives, with three nitrogen atoms, are currently prepared by copper(I)-catalyzed azide-alkyne 1,3-cycloadditions (CuAACs), commonly known as "click reactions".…”

[2.2]Paracyclophane Derivatives as Building Blocks for Coordination Polymers

“…In the past few years, our group has taken an interest in the field of MOFs, particularly in investigating new structures based on mesitylene-derived linkers [18][19][20][21][22]. Combining this with our ongoing interest in the field of [2.2]paracyclophanes [23][24][25], we decided to…”

Mesitylene Tribenzoic Acid as a Linker for Novel Zn/Cd Metal-Organic Frameworks

“…In the past few years, our interest in the field has led to several new Metal-Organic Frameworks, as well as a number of organic linkers that can be used in MOF design [24][25][26][27][28][29][30][31][32][33][34][35][36]. With the goal of obtaining novel MOFs with permanent porosity which have the potential to be used for gas storage, in this work we synthesized and characterized three new Metal-Organic Frameworks, obtained using Zn (II) and Cd (II) as metal sources and 2,4,6-tris(4carboxyphenyl)-1,3,5-trimethylbenzene (mesitylene tribenzoic acid-H 3 MTB) an organic linker which to this day, has only seen limited use in MOF design.…”