Diverse Architectures and Luminescence Properties of Group 11 Complexes Containing Pyrimidine-Based Phosphine, N-((Diphenylphosphine)methyl)pyrimidin-2-amine

Abstract

In this article, the synthesis, structural studies, and luminescence properties of Cu I , Ag I , and Au I complexes of pyrimidine-based phosphine [C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )] ( 1 ) are described. The reactions of 1 with CuX led to the isolation of one-dimensional (1D) chain, tetranuclear ladder, or cyclic derivatives. The structural features of these complexes are greatly influenced by the metal-to-ligand ratio, reaction conditions, and CuX (X = Cl, Br or I) employed. In the case of CuCl and CuBr, one-dimensional coordination polymers [{CuCl}{C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )}] ∞ ( 2 ) and [{CuBr}{C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )}] ∞ ( 3 ) were obtained, whereas CuI afforded tetracopper complex [{CuI} 4 {C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )} 2 (NCCH 3 ) 2 ] ( 4 ) having Cu 4 ladder structure supported by P∩N-bridging coordination of 1 . The reaction of 1 with AgOTf yielded unprecedented one-dimensional chain structure [{AgOTf}{C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )}] ∞ ( 5 ), whereas the reaction with AgBF 4 produced a 12-membered dinuclear complex, [{Ag}{C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )}] 2 [BF 4 ] 2 ( 6 ), with each silver atom having a linear geometry. Gold complex [{AuCl}{C 4 H 3 N 2 -2-NH(CH 2 PPh 2 )}] 2 ( 7 ) was synthesized by reacting 1 with [AuCl(SMe 2 )]. Compounds 2 – 4 were also prepared using a pestle and mortar by grinding method in almost quantitative yield. Complex 4 with a Cu···Cu distance of 2.828(5) Å shows high luminescence due to the nonbonded metal···metal interactions.

Synthesis and Photophysical Properties of Emissive Silver(I) Halogenido Coordination Polymers Composed of {Ag2X2} Units Bridged by Pyrazine, Methylpyrazine, and Aminopyrazine

“…Compared to that of copper­(I) and gold­(I) complexes, the development of luminescent silver­(I) complexes has started only recently; however, several silver complexes exhibiting strong luminescence at room temperature, − thermally activated delayed fluorescence, − thermochromic luminescence, − and stimuli-responsive luminescence , have already been reported. Because the coordination properties and electronic structures of silver­(I) complexes are similar to those of copper­(I) complexes, the ligands affording luminescent copper­(I) complexes have also been exploited to synthesize luminescent silver­(I) complexes. ,− The obtained complexes typically display emission in the near-ultraviolet (UV) or blue region even though the corresponding copper­(I) complexes show colorful emission in the visible region. ,− Because the stability of the 4d orbitals of the silver­(I) center is higher than that of the 3d orbitals of the copper­(I) center, ,− the metal-to-ligand CT ES increases in energy, approaching those of the other ESs, which causes a mixing of the ESs and complicates their emissive ESs, hampering the rational design of a ligand set for luminescent silver­(I) complexes.…”

Synthesis, structural, characterization and Hirshfeld analysis of a bisselenide and a zinc complex of a new hemilabile ferrocenylbisphosphane, [Fe{C5H4P(C6H4CH2NMe2-o)2}2]

“…In particular, phosphorus-based ligands having nitrogen-donor moieties have shown enormous potential in catalysis due to their ability to balance -donor and -acceptor properties, which directly influence the oxidative addition and reductive elimination reactions in metal-mediated catalysis (Murso & Stalke, 2004;Rokade & Guiry, 2018;Noe ¨l & Van der Eycken, 2013;Gilbertson & Xie, 1999). Our group has reported the synthesis and coordination chemistry of several P,N-donor ligands and explored their catalytic potential in organic transformations (Radhakrishna et al, 2018(Radhakrishna et al, , 2020Kumar et al, 2018;Kumaravel et al, 2014). Our group is also interested in ferrocene-based phosphorus ligands because of their unique coordination properties and catalytic potential in organic synthesis (Rao et al, 2013;Prasad & Balakrishna, 2018;Sameer Prasad et al, 2019;Siddiqui et al, 2014Siddiqui et al, , 2016Punji et al, 2007).…”

Versatile Coordination Modes of 2,6‐Bis(2‐(diphenylphosphanyl)‐1H‐imidazol‐1‐yl)pyridine in Cu(I) and Au(I) Complexes

“…[18][19][20] The ligand framework and the nature of donor atoms are very important to fabricate structure specific self-assembly and desired coordination networks. [21][22][23] The one dimensional coordination polymers are considered to be the simplest ones with interesting structural and optical properties. [24] The diversity of these structural motifs is also reflected in their photophysical properties.…”

“…[25] Some of the known 1D coordination polymers of copper(I) complexes supported by phosphine appendage with N-heterocyclic ligands are listed in Figure 1. In most of these complexes (I-V) [16,18,23,26,27] copper(I) ion show four coordinated tetrahedral arrangement. The reported compound VI is the first illustration of a rare 1D copper(I) coordination polymer stabilized by phosphine appended with N-heterocycles.…”

“…Earlier reports suggested that copper(I) ions with d 10 closed‐shell electronic configurations show high affinity towards nitrogen donors and irregular geometry with coordination numbers 2–5, which controls the self‐assembly . The ligand framework and the nature of donor atoms are very important to fabricate structure specific self‐assembly and desired coordination networks . The one dimensional coordination polymers are considered to be the simplest ones with interesting structural and optical properties .…”