Molecular Rearrangement of Trinuclear Cu(I)‐NHC: Synthesis of Mono, Binuclear and Polymeric Cu(I)‐NHCs

Abstract

A trinuclear Cu(I)‐NHC [Cu3(py2im)3](PF6)3 (1) has been synthesized in a very short period of time (5‐10 min) in multi‐gram scale using less expensive Cu(OAc)2⋅H2O and py2imH⋅PF6 in presence of L‐ascorbic acid in CH3OH under aerobic conditions at room temperature. Further, a very facile synthetic route has been developed to obtain a mononuclear [Cu(py2im)(phen)](PF6) (3), binuclear [Cu2(py2im)3](PF6)2 (2) and 1D polymeric chain of Cu(I)‐NHC {[Cu(py2im)(4,4′‐bpy)](PF6)}n (4), {[Cu(py2im)(bpe)](PF6)}n (5), {[Cu(py2im)(bpe)](PF6)}n.{[Cu2(py2im)3](PF6)}n (6) and {[Cu(py2im)(azpy)](PF6)}n (7) from a trinuclear Cu(I)‐NHC cluster (1) using additional linear bridging co‐ligands such as 4,4′‐bipyridine (bpy), trans‐1,2‐bis(4‐pyridyl)ethene (bpe), 4,4′‐azobispyridine (azpy) etc. In CH3CN, 4 and 5 were rearranged to adamantanoid core 3D Cu(I)‐MOF {[Cu(bpy)2](PF6)}n (8) and {[Cu(bpe)2](PF6)}n (9), respectively. X‐ray crystallographic structure of 6 exhibits two molecules of 2 which was trapped between two polymeric chains.

Photo‐/Electroinduced Irreversible Isomerization of 2,2’‐Azobispyridine Ligands in Arene Ruthenium(II) Complexes

“…It is also a wellknown ligand for metal center, [1] with resulting complexes used as magnetic resonance imaging probes, [2] cytotoxic agents against cancer cell, [3][4][5] or as building components in switchable materials. [6][7][8][9][10] The ligand properties of azobispyridine have been investigated towards a number of metals, such as Cd II , [11][12][13][14][15][16] Cu II , [13,15,17,18] Re I , [19][20][21] Cu I , [13,18,22] Ni II , [13,15,23] Zn II , [15,23] Ru II , [24,25] Ag I , [26,27] Co II , [11,13] Re II and Re V , [21] Pt II , [28] Hg II , [15] Au I , [26] Mn II , [13] W 0 and Os 0 , [29] and Ti II , [30] giving rise to new types of polymer structures involving π-π and π-p stacking of the ligand. [13][14][15]…”

“…[13][14][15][16]30] The coordination properties to the metal center are obviously impacted by the position of the nitrogen atom in the pyridine ring of the ligand. Linear patterns such as I and II are most common for 4,4'-and 3-3'-azobispyridine [11][12][13][14][15]19,20,22,24,27,29] (Figure 1), while bidentate coordination mode with five-membered chelate rings such as IIIa, [16][17][18]21,23,26,28] or more rarely tridentate coordination such as IIIb, are found with (E)-2,2'-azobispyridine. [31,32] A peculiar property of the latter ligand in these systems is that it usually does not undergo E/Z photoisomerization as a consequence of the geometrical constraints imposed by the strong bonding to the metal center, with one notable exception found in the case of Ag I complex.…”

Rational Design of Mixed Matrix Membranes Modulated by Trisilver Complex for Efficient Propylene/Propane Separation

“…Unlike MOFs, Ag 3 pz 3 is a 0D molecule (≈10 Å) that is soluble in many organic solvents, making it possible to prepare membrane with a molecular‐level dispersion of these fillers. [ 36 ] In addition, the Ag 3 pz 3 complex can be tailored to optimize π ‐acidity and compatibility with the polymeric matrix. Therefore, Ag 3 pz 3 is a promising material for fabricating C 3 H 6 /C 3 H 8 separation membranes.…”